Production system for synthesizing humic acid zeolite-based slow-release ecological fertilizer from coal-based organic waste and fly ash waste

Abstract

The invention discloses a production system for synthesizing a humic acid zeolite-based slow-release ecological fertilizer from coal-based organic wastes and fly ash wastes, which is characterized in that waste organic matters collected during cleaning pretreatment of carbonaceous fuel at the front end of a coal-fired boiler are used as organic raw materials for synthesizing artificial humic acid and are processed into humic acid organic polymers in situ; fly ash collected by a dust remover at the rear end of a coal-fired boiler is used as a main inorganic raw material for synthesizing the zeolite-based slow-release structure crystal material; according to the method, two kinds of solid waste from the front end and the rear end of a coal-fired thermoelectric boiler system are formed to serve as raw material feeding of the production line through cooperation with field layout of a coal-fired boiler electric power production system, the cheap humic acid composite zeolite slow-release fertilizer is produced through the solid waste of a power plant, and meanwhile macro-quantity, micro-quantity and trace-quantity beneficial mineral elements are loaded; according to the invention, links such as feeding pretreatment of two main solid waste raw materials of the coal electric boiler, processing production of the materials, loading of mineral nutrients, synthesis production of composite materials and the like are integrated into a continuous technological process of an integrated production line.

Description

[0001] This application claims the priority of a prior application titled "Production System for Synthesizing Humic Acid Zeolite-based Slow-release Ecological Fertilizer from Coal-based Organic Waste and Fly Ash Waste", with the patent application number 202311627356.3, which was filed with the China National Intellectual Property Administration on November 30, 2023. The full text of the prior application is incorporated herein by reference. Technical Field

[0002] The present invention belongs to a production system for producing agricultural slow-release ecological fertilizer using coal-based organic waste and fly ash waste; it relates to the recycling treatment technology of fly ash waste and coal-based organic waste, as well as a system integration solution for applying the waste treatment technology in the new production process of synthesizing humic acid zeolite-based slow-release ecological fertilizer; specifically, it relates to a production system that integrates industrial wastes in the coal power industry, such as organic component substances of coal (low-value lignite, including peat) and coal fly ash substances, into a new process flow through multiple recycling technology treatment units, to achieve the efficient and low-cost production of humic acid zeolite-based slow-release ecological fertilizer products. The present invention proposes using industrial wastes from coal-fired power plants as raw materials for recycling agricultural slow-release fertilizers, which can significantly reduce the cost of producing commercial humic acid organic fertilizers. By comprehensively replacing commercial chemical fertilizers that cause non-point source pollution of the soil surface with humic acid zeolite-based ecological fertilizers with slow-release macronutrients, various macro, micro, and trace beneficial mineral nutrients derived from plants can be recycled and used to nourish the healthy ecology of the soil in a cyclic manner. Background Art

[0003] The loss and overuse of chemical fertilizers will accelerate the loss of soil organic carbon content, change the pH value of the soil, and promote the increase of various ion concentrations such as Na + , Mg 2+ , Ca 2+ , Cl - , HCO 3 - and SO 4 2- in soil water, resulting in soil salinity, cultivated land degradation, and the formation of non-point source pollution of chemical fertilizer salts that have a negative impact on plant growth. The patent application with the application number 202311514088.4 discloses a humic acid zeolite-based slow-release fertilizer composed of humic acid organic substances and zeolite inorganic substances, which is an efficient ecological fertilizer that resists salt and retains water, prevents nutrient loss, can comprehensively replace commercial chemical fertilizer salts, and improve soil organic carbon content and ensure the long-term active health of the soil.

[0004] Natural zeolite is a scarce mineral resource. Materials with a structure similar to natural zeolite can be mass-produced from coal fly ash through the process of zeolitization. Most of the fly ash solid waste produced by coal-fired power plants globally (e.g., 34% of the fly ash in industrialized countries worldwide) is currently mainly used in low-value resource utilization directions, such as being used as raw materials for building materials like cement and ash bricks (including applications such as mine backfilling, geological stabilization, engineering fillers, and road bases). The high transportation cost of fly ash waste and the application direction of low-value building raw materials inevitably hinder the resource utilization of fly ash solid waste. In most cases, it is difficult for fly ash to compete with traditional mineral materials in terms of cost as a substitute raw material in building materials. Moreover, as the growth rate of demand for building materials such as cement slows down and the market approaches saturation, the opportunity for fly ash materials to generally replace traditional mineral materials decreases. As the largest industrial solid waste resource, it urgently needs to break through the technical bottlenecks in its market utilization breadth and high-value recycling.

[0005] Fly ash zeolite-based materials, as an excellent cage pore slow-release crystal material, are one of the main raw materials for producing macronutrient slow-release ecological fertilizers for agriculture. Because of their function of preventing non-point source pollution, they can generally replace the currently widely used commercial fertilizer salts (see the patent application with the application number 202310381676.9). Therefore, a technological breakthrough in the agricultural resource utilization of fly ash solid waste can create circular economic value related to the world's largest industrial solid waste.

[0006] The composite of humic acid substances and zeolite-based slow-release materials is a highly efficient ecological fertilizer that can both prevent the loss of macronutrients and prevent the degradation of arable soil and assist plants in combating salt stress. However, natural humic acid substances are organic nutrients that are generally lacking in arable soil because the process of natural humus formation in the soil is extremely slow, and agricultural arable land cannot rely on nature to maintain its soil humic acid or soil organic carbon content.

[0007] The organic carbon substance that is closest to natural humic acid substances and is the most abundant on Earth is lignocellulose, which is a natural aromatic compound rich in aromatic or aliphatic compounds and is derived from the growth of natural plant biomass; it is a three-dimensional, highly cross-linked macromolecular polymer formed by enzymatic polymerization and contains a large number of active functional groups such as methoxy, carbonyl, carboxyl, and hydroxyl groups. The emerging HTH process (HydroThermal Humification) can solve the technical problem of the natural conversion of lignin into humic acid-like organic polymers (refer to Fan Yang.et al, A hydrothermal process to turn waste biomass into artificial fulvic and humic acids for soil remediation, Science of the Total Environment, 686(2019), 1140-1151), that is, the technical problem of artificial humic acid; according to scientific calculations, the efficiency of synthesizing humic acid-like organic polymers by the HTH process is as high as 10 9 times.

[0008] Lignin is also the main component in peat and low-calorie lignite deposits in the world. The unmineralized biopolymers in lignite are mainly lignin. When it enters the boiler as fuel for combustion, it will produce a large amount of volatile organic gases (voc) and water vapor, thus reducing the overall efficiency of coal-fired power plants. Therefore, raw coal fuels such as lignite and peat rich in biopolymers such as lignin have the value of large-scale extraction of biopolymers as renewable raw materials for producing artificial humic acid materials; combining the extraction process of separating the biopolymer components contained in low-calorie lignite with the pretreatment process of cleaning and upgrading the lignite raw materials of coal-fired power plants can provide cheap raw materials required for the HTH process to synthesize artificial humic acid materials. Summary of the Invention

[0009] To improve the above technical problems, the present invention provides a new production system for a humic acid zeolite-based slow-release ecological fertilizer using industrial waste materials such as organic component substances of coal (low-value lignite, including peat) and fly ash substances from coal-fired boiler combustion as the main renewable raw materials, specifically including a production system that integrates industrial waste materials in the coal power industry such as organic component substances of coal (low-value lignite, including peat) and fly ash substances from coal-fired boiler combustion through multiple regeneration technology treatment units into a new process flow.

[0010] The present invention provides a system, including:

[0011] Unit 3 for separating modified lignin of humic acid-like substances;

[0012] Unit 4, which is downstream of the said Unit 3 and is used to convert the modified lignin of Unit 3 into artificial humic acid;

[0013] Unit 5, which is downstream of the said Unit 4 and is used to catalyze the hydrothermal humification to synthesize artificial humin;

[0014] Unit 6, which is downstream of the said Unit 5 and is used to catalyze hydrothermal carbonization; and

[0015] Unit 1, which is upstream of the said Unit 3 and is used to prepare the additives in Unit 3 and / or Unit 5 and / or Unit 6.

[0016]

Unit 1

[0017] Unit 1 is a FA-HTZ fly ash alkali fusion hydrothermal boiling process unit, which is used to synthesize the feed of the coal-fired power boiler combustion fly ash into additives. The additives are fly ash zeolite-based materials (solid acid catalytic materials) with functions such as solid acid catalysis, nutrient slow release, and large specific surface area adsorption;

[0018] Unit 1 is located at the feed end of the fly ash solid waste material at the uppermost upstream of the process flow, collecting the fly ash material. Through the (high-temperature melting and polymerization two-stage) hydrothermal boiling process in Unit 1, the fly ash (such as the fly ash in the patent application with the application number 202310400924.X) is synthesized into a compound with a FAU / Zeolite faujasite nanocrystal structure, that is, the said fly ash zeolite-based material. Due to the presence of various mineral elements and process-added elements, the output is an additive material for Unit 3 and / or Unit 5 and / or Unit 6 with chemical active functions such as solid acid catalysis, cation exchange, and large specific surface area adsorption.

[0019] In the present invention, the main raw materials for synthesizing the zeolite-based material are the combustion fly ash produced by power plants (including but not limited to the following power plants, such as coal-fired power plants, biomass power plants, carbon fuel boiler plants, etc.), as well as the fly ash from fly ash landfills and ultrafine powder raw materials prepared from boiler combustion residues; preferably, the fly ash immediately produced by the power plant pulverized coal boiler is selected.

[0020] In the present invention, the said fly ash zeolite-based material, with its unique honeycomb-like micro-mesoporous cage structure, dispersedly supports beneficial mineral elements, can provide energy and mineral elements for soil microorganisms; can be widely used as a fertilizer slow-release medium in the soil, having effects such as promoting the micro-ecological balance of the soil, promoting the degradation or inactivation of soil toxic substances, achieving the promotion of plant growth, and improving the soil.

[0021] In the present invention, the fly ash zeolite-based material can also be used as unit 5C-HTH and unit 6C-HTC respectively, that is, the solid acid catalyst for catalytic hydrothermal humification and catalytic hydrothermal carbonization (such as the solid acid catalyst in the patent application with the application number 202210886336.7), and respectively complete the modification of lignin by C-HTH catalytic hydrothermal humification combined with mineral elements; improve the carbon conversion rate of the C-HTC catalytic hydrothermal carbonization process of biomass.

[0022] In the present invention, unit 5 is used to carry out hydrothermal humification reaction (C-HTH) on materials containing organic carbon, such as humin slurry, municipal solid waste (organic solid waste), wet biomass, etc. to synthesize artificial humin, so it can also be understood as carrying out co-hydrothermal humification reaction (Co-HTH); unit 6 is used to carry out hydrothermal carbonization reaction (C-HTC) on the slurry of materials containing organic carbon, such as the slurry of humin slurry, municipal solid waste (organic solid waste), wet biomass, etc., so it can also be understood as carrying out co-hydrothermal carbonization reaction (Co-HTC).

[0023] According to an embodiment of the present invention, unit 1 is used to prepare additives in unit 3 and / or unit 5 and / or unit 6, for example, the solid acid catalyst is prepared by the fly ash alkali fusion hydrothermal zeolitization (FA-HTZ) process method.

[0024] According to an embodiment of the present invention, unit 1 includes a melting and polymerization reaction furnace, a grinding device, a dilution tank, an ultrasonic device and a hydrothermal activation device connected in sequence.

[0025] According to an embodiment of the present invention, the melting and polymerization reaction furnace is provided with a fly ash feed inlet, an additive inlet and an alkaline reagent feed inlet.

[0026] According to an embodiment of the present invention, unit 1 further includes a filtering device, and the liquid outlet of the filtering device is connected to the dilution tank through a pipeline to recycle and reuse the filtered medium liquid.

[0027] According to an embodiment of the present invention, the additive is prepared by an alkali fusion conversion method in a melting and hydrothermal two-stage manner using fly ash as a raw material.

[0028] According to an embodiment of the present invention, the preparation method of the additive includes the following steps: fly ash is melted and polymerized under alkaline conditions, the obtained polymer is ground, diluted, ultrasonically treated, and subjected to a hydrothermal activation reaction to obtain the zeolite-based solid acid catalyst.

[0029] According to an embodiment of the present invention, the alkaline condition can be provided by a strong base, for example, the strong base is potassium hydroxide and / or sodium hydroxide.

[0030] According to an embodiment of the present invention, the conditions for melting and aggregation include: a temperature of 400 - 650 °C and a time of 2 - 8 h; for example, a temperature of 450 - 550 °C and a time of 4 - 6 h.

[0031] According to an embodiment of the present invention, the polymer is ground to 0.075 mm to 0.2 mm.

[0032] According to an embodiment of the present invention, the concentration of the solid substance in the obtained mixture after dilution is 1 - 5 mol / L, for example, 2.5 mol / L.

[0033] According to an embodiment of the present invention, the diluent used for dilution is water or a liquid medium recovered from a hydrothermal activation reaction.

[0034] According to an embodiment of the present invention, fly ash is optionally added or not added during dilution.

[0035] According to an embodiment of the present invention, the time for ultrasonic treatment is 10 - 30 min, for example, 15 min.

[0036] According to an embodiment of the present invention, the conditions for the hydrothermal activation reaction include: a temperature of 70 - 100 °C and a time of 2 - 8 h; for example, a temperature of 80 - 90 °C and a time of 4 - 8 h.

[0037] Alternatively, the preparation method of the additive includes the following steps: the fly ash undergoes a zeolitization process synthesized by two - stage fusion (melting, hydrothermal) to prepare the nano - composite zeolite material.

[0038] According to an embodiment of the present invention, the process of the melting stage includes: mixing fly ash with an alkali, heating and melting, grinding, and diluting to obtain a pre - crystallization precursor solution.

[0039] Among them, the alkali is selected from strong alkalis, such as sodium hydroxide.

[0040] Among them, the temperature for heating and melting can be 500 - 600 °C and the time is 1 - 9 h.

[0041] According to an embodiment of the present invention, the process of the hydrothermal stage includes: an aging and hydrothermal process to obtain crystals; or includes: adding doping elements, aging, and hydrothermal process to obtain crystalline composite - element crystals.

[0042] According to an embodiment of the present invention, the hydrothermal stage may include a repeated hydrothermal process of adding N doping elements, where N is an integer equal to or greater than 1, for example, N = 1, 2, 3, 4, 5, 6, 7, 8, 9, 10.

[0043] According to an embodiment of the present invention, doping elements are added, preferably before the start of the hydrothermal process with N>1, to introduce specified elements and uniformly form highly active catalytic sites with these elements.

[0044] According to an embodiment of the present invention, the doping elements are introduced through the following dopants, including but not limited to nanoparticles of the one, two or more doping elements, alkalis, and / or crystal nuclei, etc.

[0045] According to an embodiment of the present invention, the dopant is added to the crystallization precursor solution, but when N = 1 and N≥2, the preparation of the crystallization precursor solution is different:

[0046] When N = 1, the crystallization precursor solution is obtained by mixing fly ash with an alkali, or further mixing with a dopant, heating and melting, grinding, and diluting.

[0047] When N≥2, the crystallization precursor solution is obtained by mixing the filtrate obtained after the completion of the previous hydrothermal crystallization stage with a dopant, and adding or not adding an alkali as needed, and then mixing and diluting.

[0048] According to an embodiment of the present invention, the mass ratio of the dopant to the crystallization precursor solution is 1:(1 to 5), such as 1:1, 1:2, 1:3, 1:4 or 1:5.

[0049] According to an embodiment of the present invention, the temperature of the hydrothermal process is 90 to 170 °C, and the time is 2 to 48 h.

[0050] According to an embodiment of the present invention, the solid acid catalyst can be the fly ash zeolite-based composite oxygen carrier described in Chinese Patent Application No. 202311217726.6.

[0051] According to an embodiment of the present invention, the fly ash is the fine ash particles discharged during the fuel combustion process, optionally containing or not containing unburned carbonaceous particles. Fly ash containing unburned carbonaceous particles is also called fly ash or soot. In a preferred embodiment, the fly ash is taken from the combustion fly ash produced by a power plant (including but not limited to the following power plants, such as coal-fired power plants, biomass power plants, carbon fuel boiler plants, etc.), as well as fly ash from fly ash landfills and ultrafine powder raw materials prepared from boiler combustion residues; preferably, the fly ash immediately produced by a power plant pulverized coal boiler is selected, and preferably the fly ash collected by the dust collector at the backend of a coal-fired boiler.

[0052] According to an embodiment of the present invention, the oxygen carrier is prepared from fly ash. Preferably, the oxygen carrier is the oxygen carrier with a dual-phase catalytic function used in the novel chemical looping combustion (application number 202311472824.4).

[0053] According to an embodiment of the present invention, the oxygen carrier comprises a metal oxide and a support, wherein the support is a fly ash zeolite-based support. Preferably, the metal oxide is dispersed in the support. For this purpose, a powder form of the metal oxide or a metal oxide containing a dispersant can be used to add it dispersedly to the crystallization precursor solution. For example, dispersed in a fly ash zeolite-based microporous aluminosilicate crystallization precursor solution, the metal oxide is uniformly distributed (or dispersed) and supported in the crystal structure of the support through the crystallization process.

[0054] Those skilled in the art should understand that when a dispersant is used, the dispersant can be selected from the dispersants known to those skilled in the art as long as it helps to disperse the metal oxide in the crystallization precursor solution of the support.

[0055] According to an embodiment of the present invention, the solid acid catalyst has a crystal structure of FAU zeolite.

[0056] According to an embodiment of the present invention, the addition of the metal oxide includes but is not limited to oxides of two or more metals selected from the following metals: potassium, sodium, magnesium, iron, zinc, chromium, manganese, cobalt, nickel, copper, aluminum, lead, manganese, zirconium, tin, zinc, tungsten, molybdenum, and vanadium; preferably iron oxide, zinc oxide, and aluminum oxide; as an example, the metal oxide is iron(III) oxide, zinc oxide, and aluminum oxide.

[0057] According to an embodiment of the present invention, when the metal oxide is iron(III) oxide, it may have a nanocrystalline particle structure of γ-Fe 2 O 3 、α-Fe 2 O 3 、γ-Fe 3 O 4 。

[0058] According to an embodiment of the present invention, the metal of the metal oxide is derived from the metal contained in the fly ash itself, or an externally added metal or metal oxide. For example, the metal contained in the fly ash itself comes from the metal in the material containing organic carbon.

[0059] Those skilled in the art should understand that at the start of the treatment system, metal elements, i.e., metal oxides, can be added to the fly ash in unit ○1 as needed to make the solid acid catalyst have a sufficient amount of metal oxide. After the treatment system is in steady-state operation, when the metal elements circulate in the combustion system through oxidation and reduction reactions, no additional metal or metal oxide needs to be added. For this purpose, units 3, 4, 5, 6, and 1 of the treatment system of the present invention are each closed, and the connecting pipelines between units 3, 4, 5, 6, and 1 are closed.

[0060] According to an embodiment of the present invention, the addition of the metal oxide may be nanoparticles. For example, the size of the nanoparticles is 0.1 - 100 nm, such as 1 - 50 nm, and exemplarily 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50 nm.

[0061] According to an embodiment of the present invention, the metal oxide nanoparticles are iron oxide nanoparticles with a particle size of 3 - 5 nm.

[0062] According to an embodiment of the present invention, the particle shape of the metal oxide may be circular, ellipsoidal or other regular or irregular shapes.

[0063] According to an embodiment of the present invention, the oxygen carrier is a micro-nano material, that is, it has a micro-nano crystal structure.

[0064] According to an embodiment of the present invention, the mass ratio of the addition of the metal oxide to the zeolite-based solid acid catalyst is 5 - 35 wt%, such as 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%.

[0065] According to an embodiment of the present invention, the particle size of the solid acid catalyst is 0.075 mm - 0.2 mm, such as 100 μm, 120 μm, 150 μm, 180 μm.

[0066] According to an embodiment of the present invention, the solid acid catalyst or oxygen carrier is prepared from fly ash as a raw material by an alkali conversion method in a two-stage process of melt polymerization (molten polymerization) - hydrothermal treatment.

[0067] According to an embodiment of the present invention, the solid acid catalyst or oxygen carrier further includes one or more metal complexes or non-metal complexes, which are mainly used to modify or promote the catalytic function of the active metal elements in the metal oxide nanoparticles and / or the oxygen carrier, such as being able to cooperate or compensate with the functions of these metal elements.

[0068] According to an embodiment of the present invention, the metal elements of the metal complexes may be selected from rare earth metal elements and / or semi-metal elements; for example, the rare earth metal elements are lanthanum (La) and cerium (Ce) elements, preferably cerium element; for example, the semi-metal element is silicon (Si).

[0069] According to an embodiment of the present invention, the metal complexes may also be selected from metal compounds such as ruthenium, nickel, palladium, silver, platinum, nickel, cobalt, vanadium, aluminum, chromium, copper, zinc, molybdenum, tin, manganese, gold, rhodium, zirconium, tungsten, rhenium, osmium, iridium, titanium, etc., preferably compounds of aluminum and zinc, more preferably aluminum oxide and zinc oxide.

[0070] In one embodiment, the rare earth metal element is derived from its salt or oxide, and the metalloid element is derived from its oxide (such as silicon dioxide).

[0071] In one embodiment, the metal compound is the corresponding metal salt or oxide.

[0072] According to an embodiment of the present invention, the metal complex is a nanoscale metal oxide, such as nanoceria, nanoaluminum oxide, and / or nanozinc oxide.

[0073] According to an embodiment of the present invention, the size of the metal oxide nanoparticles and / or metal complexes is less than 300 nm, preferably less than 200 nm, more preferably less than 100 nm, and still more preferably less than 30 nm, 10 nm, 4 nm.

[0074] According to an embodiment of the present invention, the solid acid catalyst can be the nanocomposite zeolite material described in Chinese Patent Application No. 202310381676.9.

[0075] According to an embodiment of the present invention, the nanoscale crystal structure of the nanocomposite zeolite material is the FAU / Zeolite structure, preferably the FAU / Zeolite Y type structure.

[0076] According to an embodiment of the present invention, the nanocomposite zeolite material has a micro-mesoporous cage-frame void space.

[0077] According to an embodiment of the present invention, the nanocomposite zeolite material is an aluminosilicate hydrate.

[0078] According to an embodiment of the present invention, the nanocomposite zeolite material further contains one, two, or more of the following elements: magnesium (Mg), iron (Fe), zinc (Zn), molybdenum (Mo), boron (B), selenium (Se), etc. Preferably, the element is added to the crystallization precursor solution of the zeolitization process in the form of its chloride (such as zinc chloride, iron chloride).

[0079] According to an embodiment of the present invention, the nanocomposite zeolite material is of the faujasite type structure (FAU).

[0080] According to an embodiment of the present invention, the nanocomposite zeolite material has a three-level pore structure: the pore diameter of the first-level pore structure does not exceed 10 nm, such as not exceeding 5 nm, and is still more preferably less than 2 nm (i.e., micropores); the pore diameter of the second-level pore structure (also called mesopores) is equal to or greater than the pore diameter of the first-level pore structure and does not exceed 50 nm; the pore diameter of the third-level pore structure (also called macropores) is greater than 50 nm, such as greater than 50 nm and not exceeding 500 nm, for example, 200 nm.

[0081] According to an embodiment of the present invention, the sum of the specific surface areas of the nano-composite zeolite material is 150 - 1500 m 2 / g, for example 300 - 1200 m 2 / g, still for example 500 - 1000 m 2 / g.

[0082] According to an embodiment of the present invention, the cation exchange capacity (CEC, Cation Exchange Capacity) of the nano-composite zeolite material is 150 - 250 cmol(+) / kg.

[0083] According to an embodiment of the present invention, the proportion of the pore volume of the nano-composite zeolite material exceeds 50%, for example exceeds 60%, such as 65 - 80%.

[0084] According to an embodiment of the present invention, the mass density of the nano-composite zeolite material is 2.1 - 2.2 g / cc.

[0085] According to an embodiment of the present invention, the nano-composite zeolite material has water-holding performance (water retention performance 50 wt%).

[0086] According to an embodiment of the present invention, the nano-composite zeolite material is insoluble in water at any pH. Alternatively, the nano-composite zeolite material has acid and alkali resistance characteristics, that is, it is neither soluble in alkali (high pH) nor soluble in acid (low pH).

[0087] According to an embodiment of the present invention, the fly ash includes but is not limited to one, two or more of the following sources: combustion fly ash produced by power plants (including but not limited to the following power plants, such as: coal-fired power plants, biomass power plants, carbon fuel boiler plants, etc.), fly ash from fly ash landfills, and ultrafine powder raw materials prepared from boiler combustion residues; preferably, fly ash immediately generated by a power plant pulverized coal boiler is selected, and preferably fly ash collected by a dust collector at the rear end of a coal-fired boiler.

[0088] According to an embodiment of the present invention, after the hydrothermal activation reaction is completed, the product is filtered, washed, and dried to obtain the additive (such as an oxygen carrier). The solid acid catalyst fly ash zeolite-based material synthesized by unit 1 can also be used as a slow-release carrier for macronutrients (such as: K + or NH 4 + 、NO 3 - ), and has the special function of sequentially releasing nutrient cations in soil water and exchanging cations such as Na + 、Ca 2+ in soil water. The loaded macronutrients only slowly release nutrient cations and exchange and absorb Na according to the inherent preference order of cation exchange in the zeolite structure.+ or Ca 2+ reduce soil salinization; The fly ash synthesized zeolite-based material, with its unique honeycomb-like micro-mesoporous cage structure, dispersedly supports beneficial mineral elements and provides energy and mineral elements for soil microorganisms; When widely used as a fertilizer slow-release medium in the soil, it can promote the soil micro-ecological balance, promote the degradation or inactivation of soil toxic substances, and achieve effects such as promoting plant growth and improving the soil.

[0089] The fly ash synthesized zeolite-based material can also be used as the solid acid catalyst in Unit 6, namely catalytic hydrothermal carbonization; In the C-HTC liquid-phase reaction of Unit 6, it can catalyze the carbon conversion rate of the hydrothermal pretreatment process.

[0090]

Unit 2

[0091] According to an embodiment of the present invention, the system further includes Unit 2 for pulping raw material materials containing lignin such as peat, lignite, and wet biomass.

[0092] Unit 2 is a wet biomass processing and pulping unit for pulping feed raw materials containing lignin components such as peat, lignite, and wet biomass.

[0093] According to an embodiment of the present invention, the system further includes an auxiliary pulping processing unit 2' for wet biomass materials that cannot be used in agricultural fertilizers, such as: municipal sludge, etc., including organic sludge contaminated with heavy metals.

[0094] According to an embodiment of the present invention, Unit 2 and Unit 2' are located at the feeding ends of bulk organic materials such as lignite and peat at the upstream of the production process flow, to pulp the organic materials containing lignin components according to industrial standards; At the same time, the organic slurry containing heavy metals or unsuitable ones is removed from the fertilizer product processing link, and is pulped by the auxiliary pulping processing unit 2' for producing additives for catalytic combustion assistance and oxygen-carrying fuel auxiliary raw materials.

[0095] In the present invention, the wet biomass for Unit 2 refers to the plant biomass formed through photosynthesis, including but not limited to the biomass waste formed in the past: agricultural and forestry waste, agricultural product processing leftovers, poultry and livestock manure, kitchen waste, the organic components in peat (peat contains more than 60% lignin), etc.; The residues composed of plants and other biomass are the most massive biological renewable resources on the earth (the order of magnitude is hundreds of billions of tons / year); A very small part used to produce "artificial humic acid" is sufficient to compensate for the annual loss of soil organic carbon globally. Biomass pulping is a traditional process for transforming organic materials into industrial raw materials.

[0096] According to an embodiment of the present invention, Unit 2 is provided with feeding inlets for peat, lignite, and other raw materials rich in lignocellulose.

[0097] According to an embodiment of the present invention, the unit 2 is provided with an outlet for the single coal water slurry.

[0098] According to an embodiment of the present invention, the unit 2' is provided with an inlet for municipal sludge or other heavy metal-exceeding organic sludge.

[0099] According to an embodiment of the present invention, the unit 2' is provided with an outlet for municipal sludge homogenate.

[0100]

Unit 3

[0101] Unit 3 is a CAFT (Catalytic Alkali Fenton Treatment) alkali lye Fenton catalytic modification unit, which is used to make bulk raw materials of peat and lignite into lignin raw pulp. Through the heterogeneous Fenton reaction of lignin humification, amphiphilic aggregates and fulvic acid liquid are separated to produce Fenton-catalyzed modified lignin alkali pulp.

[0102] Unit 3 is located downstream of the outlet end of the solid acid catalytic material of Unit 1 and downstream of the outlet end of the coal water slurry. It is used to mix the zeolite-based solid acid catalytic material from Unit 1 into the lignin particles of the coal slurry and mix with the additive feed H 2 O 2 , and alkaline reagents such as NaOH are mixed to undergo a high-density free radical reaction, quickly strengthening the formation of an aggregation pattern of amphiphilic groups, that is, separating modified lignin precipitates similar to humic acid substances that can stimulate plants to produce tolerance to salt-induced abiotic stress. Various beneficial mineral elements such as iron oxide contained in the zeolite-based from Unit 1 are doped and deposited in the mixed precipitate of the separated lignin polymer and zeolite crystal, promoting the composite precipitation of lignin particles and zeolite crystal doped with mineral elements. The zeolite-based solid acid catalytic material will always maintain the pore cage adsorption structure and stable catalytic activity in all subsequent (i.e., not exceeding 300 °C) liquid-phase reaction environments.

[0103] The water storage performance of the soil humic acid substance structure will be damaged due to water loss at any time, but the zeolite structure with a water content of 50 wt% is a stable hydrate material. The composite material combined with humic acid can synergistically enhance the water holding capacity in the soil and form a reversibly recoverable water storage stable structure.

[0104] According to an embodiment of the present invention, the unit 3 is used to use the fly ash zeolite-based solid acid catalyst and the like prepared in the unit 1 as a Fenton reaction catalytic material to strengthen the liquid-phase reaction of high-density free radicals incorporated into lignin particles, quickly forming an aggregation pattern of amphiphilic groups, that is, separating modified lignin similar to humic acid substances that can stimulate plants to produce tolerance to salt-induced abiotic stress.

[0105] According to an embodiment of the present invention, the unit 3 includes a Fenton reaction sizing device, a microwave device, and an extraction device that are connected in sequence.

[0106] According to an embodiment of the present invention, the Fenton reaction sizing device is provided with a biomass raw material inlet, an additive (solid acid catalytic material) inlet, and an alkaline reagent inlet.

[0107] According to an embodiment of the present invention, the biomass raw material is selected from organic waste obtained by pre-cleaning treatment before combustion of traditional boiler fuels (including low-value lignite, peat, biomass).

[0108] According to an embodiment of the present invention, the alkaline reagent can be provided by a solution of a strong base combined with H 2 O 2 The strong base is potassium hydroxide and / or sodium hydroxide.

[0109] According to an embodiment of the present invention, a solid-liquid separation device, such as a centrifuge, is further provided downstream of the microwave device. Preferably, the outlet of the mixed material of the microwave device is connected to the inlet of the solid-liquid separation device to separate the solid-phase material and the liquid-phase material of the Fenton catalytic reaction in the mixed material of the microwave device.

[0110] According to an embodiment of the present invention, the solid-liquid separation device is provided with at least one outlet for the solid-phase material of the Fenton catalytic reaction to provide a solid-phase product of the Fenton catalytic reaction.

[0111] According to an embodiment of the present invention, the solid-liquid separation device is provided with at least one outlet for the liquid-phase material of the Fenton catalytic reaction to provide a liquid-phase product of the Fenton catalytic reaction.

[0112] According to an embodiment of the present invention, the unit 3 further includes a filtration device, the inlet of the filtration device is connected to the outlet of the extraction device; the liquid outlet of the filtration device is connected to the unit 5 through a pipeline to reuse the water-carbon slurry obtained by filtration.

[0113] According to an embodiment of the present invention, the product of the unit 3 is a Fenton-catalytically modified lignin slurry containing fulvic acid liquid, humic acid liquid, and a humic acid-like substance that can stimulate plants to produce tolerance to salt-induced abiotic stress.

[0114] According to an embodiment of the present invention, the product of the unit 3 can be pressure-filtered to prepare a modified lignin slurry of a humic acid-like substance.

[0115] According to an embodiment of the present invention, the unit 3 may further include a storage device for storing the obtained humic acid product.

[0116] According to an embodiment of the present invention, the additive is prepared by a two-stage alkali conversion method of melting polymerization-hydrothermal treatment using fly ash as a raw material. Exemplarily, the additive is prepared by Unit ○1.

[0117] The inventors designed a Unit 3 Fenton fly ash zeolite-based catalytic reaction, which uses the zeolite-based material synthesized from fly ash in Unit 1 as a catalyst, including but not limited to adding iron oxide zeolite-based materials, etc., deposited in a separated lignin matrix, and lignin particles modified by the Fenton reaction promoted by the zeolite-based material; doping beneficial mineral elements, in a soil formation environment similar to natural humic acid, lignin is separated and undergoes composite precipitation with crystal particles of a zeolite-based cage-frame pore structure containing various beneficial mineral elements.

[0118] The zeolite-based material has a chemically highly stable cage-frame pore crystal structure, which will "permanently" exist in the subsequent synthesis process of artificial humic acid materials and the application form of the final composite product. As a hydrated crystal structure material of aluminosilicate, 50 wt% of its water retention buffer structure is also permanent. Because the impact of drought on the water retention structure of soil humic acid substances is irreversible, that is, the water storage buffer structure of humic acid substances will be damaged due to water loss at any time, but the permanent combination with the zeolite-based material can "complement" the water retention in the soil, and can synergistically enhance the water holding capacity of the composite material, and still retain a reversibly recoverable water storage buffer after drought water loss.

[0119]

Unit 4

[0120] Unit 4 is an HTH artificial humic acid process synthesis unit, which is used for the alkali solution hydrothermal humification reaction process of synthesizing artificial humic acid, and simultaneously completes the synthesis of artificial humic acid from lignin and the separation of humin.

[0121] Unit 4 is located downstream of the unit discharge port, and converts biomass into artificial humic acid materials through "HydroThermal Humification (HTH)".

[0122] Natural humic acid is a product of the degradation and transformation of biomass through natural biological, physical, and chemical processes. Through the copolymerization reaction of the HTH process, lignin can be transformed into a humus-like polymer. The polymer combines with soil minerals to form a soil humic acid complex, which can obtain stability on a time scale of thousands of years. The solid acid catalytic material produced by Unit 1 contains elements similar to soil minerals, is mixed in the Fenton-catalyzed modified lignin slurry produced by Unit 3, enters the HTH device of Unit 4, provides various beneficial mineral elements required to complete the copolymerization reaction and molecular composition modification of lignin, and through the HTH of Unit 4, lignin is transformed into a polymer with approximate ion exchange activity of natural humic acid.

[0123] According to an embodiment of the present invention, the unit 4 is used for hydrothermal humification (HTH) reaction, and biomass can be efficiently converted into artificial humic acid materials.

[0124] According to an embodiment of the present invention, the unit 4 may further include a feeding device to provide a reaction substrate for the hydrothermal humification device. For example, the feeding device is a feeding device for solid-liquid mixed materials. Exemplarily, the product of unit 3, the Fenton-catalyzed modified lignin pulp, enters unit 4 through the feeding device.

[0125] According to an embodiment of the present invention, the unit 4 can be used to process materials containing organic carbon, such as the Fenton-catalyzed modified lignin slurry organic materials produced by unit 3.

[0126] According to an embodiment of the present invention, the unit 4 may further include a steam generating device to provide the steam required for the hydrothermal humification reaction for the hydrothermal humification device.

[0127] According to an embodiment of the present invention, the unit 4 further includes a spiral flow controller to promote the reaction in the hydrothermal humification device.

[0128] According to an embodiment of the present invention, the hydrothermal humification device is preferably a horizontal tube reaction device.

[0129] According to an embodiment of the present invention, the hydrothermal humification device is provided with at least one air inlet so that the steam in the steam generating device enters the hydrothermal humification device.

[0130] According to an embodiment of the present invention, a hydrothermal humification product separation device is further provided downstream of the hydrothermal humification device to separate the gas-phase material from the non-gas-phase material in the material produced by the hydrothermal humification device.

[0131] According to an embodiment of the present invention, a hydrothermal humification gas-phase treatment device is further provided downstream of the hydrothermal humification product separation device. The hydrothermal humification gas-phase treatment device may include a second gas-phase cooling device and / or a second gas-phase purification device, preferably including a second-phase cooling device and a second gas-phase purification device.

[0132] According to an embodiment of the present invention, the hydrothermal humification device may also be provided with at least one hydrothermal humification gas-phase material outlet and at least one hydrothermal humification solid-liquid-gas mixed material outlet. Preferably, the outlet of the hydrothermal humification gas-phase material of the hydrothermal humification device is connected to the inlet of the second gas-phase cooling device and / or the second gas-phase purification device of the hydrothermal humification gas-phase treatment device to cool and / or purify the hydrothermal humification gas-phase material.

[0133] According to an embodiment of the present invention, the outlet of the hydrothermal humification solid-liquid-gas mixed material of the hydrothermal humification device is connected to the inlet of the hydrothermal humification product separation device.

[0134] According to an embodiment of the present invention, the hydrothermal humification product separation device is provided with at least one outlet for hydrothermal humification gas-phase material and at least one outlet for hydrothermal humification solid-liquid-gas mixed material. Preferably, the outlet of the hydrothermal humification gas-phase material is connected to the inlet of the second gas-phase cooling device and / or the second gas-phase purification device to cool and / or purify the hydrothermal humification gas-phase material.

[0135] According to an embodiment of the present invention, the condensate obtained by cooling the hydrothermal humification gas-phase material can be mixed with the material provided by the feeding device. For example, it can be mixed with the material provided by the feeding device in the raw material mixer. Therefore, the hydrothermal humification gas-phase treatment device can be connected to the raw material mixer through a liquid-phase conveying pipeline.

[0136] According to an embodiment of the present invention, the hydrothermal humification gas-phase treatment device can be connected to the discharge device through a gas-phase conveying pipeline so that the gas obtained after being treated by the hydrothermal humification gas-phase treatment device enters the discharge device for discharge.

[0137] According to an embodiment of the present invention, the hydrothermal humification solid-liquid-gas mixed material contains a mixture of solid material, liquid material and gas material.

[0138] According to an embodiment of the present invention, a solid-liquid separation device, such as a centrifuge, is further provided downstream of the hydrothermal humification product separation device. Preferably, the outlet of the hydrothermal humification solid-liquid-gas mixed material is connected to the inlet of the solid-liquid separation device to separate the hydrothermal humification solid-phase material and the hydrothermal humification liquid-phase material in the hydrothermal humification solid-liquid-gas mixed material.

[0139] According to an embodiment of the present invention, the solid-liquid separation device is provided with at least one outlet for hydrothermal humification solid-phase material to provide a hydrothermal humification solid-phase product such as humin slurry.

[0140] According to an embodiment of the present invention, the solid-liquid separation device is provided with at least one outlet for hydrothermal humification liquid-phase material to provide a hydrothermal humification liquid-phase product such as humic acid liquid.

[0141] According to an embodiment of the present invention, a heavy metal separation device is provided downstream of the solid-liquid separation device. Preferably, the heavy metal separation device can separate heavy metals in the hydrothermal humification liquid-phase product by physical methods (such as adsorption method) and / or chemical methods known to those skilled in the art. Therefore, the heavy metal separation device can be a heavy metal physical separation device and / or a heavy metal chemical separation device.

[0142] As an example, an adsorbent or a filtering material, such as an ion exchange resin or a filtering membrane, is provided in the heavy metal separation device to achieve the separation of heavy metals.

[0143] According to an embodiment of the present invention, the temperature of the material entering the catalytic hydrothermal humification device through the buffer separation device is lower than the temperature of the material before entering the buffer separation device.

[0144] According to an embodiment of the present invention, the unit 4 is further provided with a heat recovery device to use the heat released by the system for preheating the material provided by the feeding device. For example, the preheating can be achieved by an additionally provided recovery preheater. As an example, the catalytic hydrothermal humification device can be provided with a heat recovery device. The heat recovery device can be a heat recovery unit or a waste heat recovery unit known in the art.

[0145] According to an embodiment of the present invention, the unit 4 further includes more than one conveying device to convey one, two or three of the above-mentioned gas-phase material, solid-phase material, and gas-phase material to the corresponding devices of the unit 4 for treatment. Preferably, such a conveying device can be provided between every two devices. Those skilled in the art should understand that such a conveying device is known in the art, and thus the present invention does not particularly limit the specific structure of the conveying device, as long as it can effectively convey the material to the desired device.

[0146] According to an embodiment of the present invention, when it is necessary to cool the material, circulating water can be selected for cooling. For this purpose, the cooling device of the present invention can also be provided with a pipeline for circulating cooling water.

[0147] According to an embodiment of the present invention, the reaction temperature in the catalytic hydrothermal humification device can be about 150 - 230 °C, such as 180 - 200 °C; the reaction time can be about 30 - 300 min, for example 60 - 120 min.

[0148] According to an embodiment of the present invention, the product of the unit 4 includes humic acid liquid and humin slurry.

[0149] According to an embodiment of the present invention, the product of the unit 4 can pass through a pressure filtration, drying, and / or granulation device to efficiently convert biomass into an artificial humic acid biopolymer material similar to humus.

[0150] According to an embodiment of the present invention, the unit 4 can further include a storage device for storing the obtained humin slurry, humic acid composite zeolite-based synthetic material, and humic acid liquid product.

[0151] The "HydroThermal Humification (HTH)" process is a chemical process that efficiently converts biomass into artificial humic acid materials. Natural humic acid is a product of the degradation and transformation of biomass through the biological, physical, and chemical processes of nature. The humic acid complex formed by the combination of humic acid and soil minerals can stabilize the organic carbon in the soil for thousands of years. Lignin is converted into humus-like polymers through the HTH process in Unit 4 under copolymerization. The product of this biopolymer can also be modified in terms of its molecular composition and molecular weight by adding solid acid catalytic materials, that is, in the process of synthesizing humic acid through HTH or HTC, the molecular composition and molecular weight of the product can be modified by adding solid acid catalytic materials to make the synthesized material have higher activity of biological redox interaction, meeting the requirements for the active quality of humic acid products.

[0152]

Unit 5

[0153] Unit 5 is the catalytic hydrothermal humification process unit of C-HTH (C-HydroThermal Humification, C-HTH) for the synthesis of modified hydrochar (artificial humin). Under the action of two types of catalytic materials, namely solid acid catalysts and biodegraded slurry, modified hydrochar with properties similar to natural humin can be synthesized.

[0154] Unit 5 is located downstream of the discharge of Unit 4 and is connected to the discharge ports of upstream Unit 2 and Unit 1.

[0155] Unit 5 is a catalytic hydrothermal humification unit designed for a variety of reaction materials. This unit can modify and adjust the humin slurry from Unit 4 with solid acid catalysts to separately process biomass reaction materials with high salt content and low salt content. Humin is modified by the added solid acid catalyst in the C-HTH process and is converted into a carbon compound with a sponge-like structure, namely modified hydrochar. The properties of modified hydrochar are similar to those of natural humin and can provide the energy and mineral requirements for soil microorganisms and soil animals. The mixture of modified hydrochar and humic acid can more stably or effectively assist in the degradation or inactivation of toxic substances in the soil; the modified hydrochar prepared by this unit combined with humic acid can buffer the soil pH and release carbon dioxide, playing a role in buffering the hydrogen ion concentration in the soil. The composition of modified hydrochar, humic acid, and / or organic carbon medium nutrients can be widely used in soil improvement, promoting the ecological balance of soil microorganisms and soil animals, promoting the degradation or inactivation of toxic substances in the soil, pH buffering and regulation, plant fertilizers, promoting plant growth, plant irrigation, etc., and can achieve good results.

[0156] According to an embodiment of the present invention, the unit 5 is used to catalyze the hydrothermal humification (C-HTH) reaction to produce artificial humin.

[0157] According to an embodiment of the present invention, the unit 5 includes a catalytic hydrothermal humification device, or includes a depolymerization device and a catalytic hydrothermal humification device disposed downstream of the depolymerization device.

[0158] According to an embodiment of the present invention, the catalytic hydrothermal humification device is disposed downstream of the depolymerization device, so that the biomass material is processed by the catalytic hydrothermal humification device after being processed by the depolymerization device; alternatively, the material can also directly enter the catalytic hydrothermal humification device for processing.

[0159] Those skilled in the art should understand that the setting of the catalytic hydrothermal humification device downstream of the depolymerization device described herein not only includes the manner of directly processing the material produced by the depolymerization device through the catalytic hydrothermal humification device, but also includes the manner of directly entering the material into the catalytic hydrothermal humification device for processing, or the manner of first processing the material produced by the depolymerization device through other devices and then processing it through the catalytic hydrothermal humification device. The above different manners should all be understood as optional manners covered by "the catalytic hydrothermal humification device is disposed downstream of the depolymerization device". Therefore, according to an embodiment of the present invention, the depolymerization device and the catalytic hydrothermal humification device can be directly connected or not directly connected.

[0160] According to an embodiment of the present invention, a buffer separation device and / or other devices can be provided between the depolymerization device and the catalytic hydrothermal humification device downstream thereof. For example, when the depolymerization device and the catalytic hydrothermal humification device are not directly connected, the material produced by the depolymerization device can be first processed by the buffer separation device or other devices and then processed by the catalytic hydrothermal humification device.

[0161] According to an embodiment of the present invention, the buffer separation device can be a gas-liquid buffer separator, such as a gas-liquid buffer separator known to those skilled in the art.

[0162] According to an embodiment of the present invention, the unit 5 can further include a feeding device to provide a reaction substrate for the depolymerization device. For example, the feeding device is a feeding device for a solid-liquid mixed material (such as 1. humin slurry; 2. solid acid catalytic material; 3. wet biomass homogenate without municipal sludge).

[0163] According to an embodiment of the present invention, the solid-liquid mixed material contains organic carbon.

[0164] According to an embodiment of the present invention, the unit 5 can be used to process materials containing various organic carbons, such as humin slurries, agricultural residues (biomass solid waste), wet biomass, etc. For example, the materials containing organic carbon can be selected from humin slurries, wet biomass homogenates without municipal sludge, food waste, kitchen waste, animal digestive fluid manure, water body bottom mud, wood waste residues, crop straws, peat, lignite, bituminous coal, etc., including one, two or more mixtures of the above organic carbon materials.

[0165] For example, when the materials containing organic carbon are selected from food waste, kitchen waste, animal digestive fluid manure, water body bottom mud, wood waste residues, crop straws, etc., they can be depolymerized first and then catalytically carbonized. Or, when the materials containing organic carbon are selected from humin slurries, wet biomass homogenates without municipal sludge, peat, lignite, bituminous coal, etc., they can be directly catalytically carbonized.

[0166] According to an embodiment of the present invention, the depolymerization device can be provided with at least one feed inlet to enable the materials provided by the feeding device to enter the depolymerization device.

[0167] According to an embodiment of the present invention, the materials in the feeding device can directly enter the depolymerization device. Or as another option, a raw material mixer, a preheating mixer, and / or a mixing storage tank are provided between the feeding device and the depolymerization device, so that the materials in the feeding device pass through the raw material mixer, the preheating mixer, and / or the mixing storage tank and then enter the depolymerization device.

[0168] According to an embodiment of the present invention, the unit 5 can further include a steam generating device to provide the steam required for the depolymerization reaction for the depolymerization device.

[0169] According to an embodiment of the present invention, the steam generating device can also provide the steam required for the reaction for the catalytic hydrothermal humification device.

[0170] According to an embodiment of the present invention, the depolymerization device can be provided with at least one steam inlet to enable the steam in the steam generating device to enter the depolymerization device.

[0171] According to an embodiment of the present invention, the depolymerization device can also be provided with at least one additive feed inlet to enable the additives required for the depolymerization reaction to enter the depolymerization device.

[0172] Or as another option, the additives can also enter the depolymerization device through the feed inlet of the solid-liquid mixed materials as long as they can participate in the depolymerization reaction.

[0173] According to an embodiment of the present invention, the depolymerization device can also be provided with at least one depolymerization gas-phase material outlet and at least one depolymerization non-gas-phase material outlet.

[0174] Preferably, the depolymerized gaseous material includes the tail gas generated by the depolymerization reaction, and the depolymerized non-gaseous material includes a mixture of solid and liquid materials that need to be further processed in a buffer separation device and / or a catalytic carbonization device after being processed by the depolymerization device.

[0175] According to an embodiment of the present invention, the depolymerized gaseous material outlet of the depolymerization device is connected to the inlet of the depolymerized gaseous material processing device. The depolymerized gaseous material processing device may include a first-phase cooling device and / or a first gaseous purification device, preferably including a first-phase cooling device and a first gaseous purification device.

[0176] According to an embodiment of the present invention, the condensate obtained by cooling the depolymerized gaseous material can be mixed with the material provided by the feeding device, for example, it can be mixed with the material provided by the feeding device in a raw material mixer.

[0177] According to an embodiment of the present invention, the depolymerized gaseous material processing device may be connected to an emission device so that the gas obtained after being processed by the depolymerized gaseous material processing device enters the emission device for emission.

[0178] According to an embodiment of the present invention, the unit 5 further includes a spiral flow controller to promote the reaction in the depolymerization device and / or the catalytic hydrothermal humification device.

[0179] According to an embodiment of the present invention, the depolymerization device and / or the catalytic hydrothermal humification device is preferably a horizontal tube reaction device.

[0180] According to an embodiment of the present invention, the catalytic hydrothermal humification device is provided with at least one air inlet so that the steam in the steam generation device enters the catalytic hydrothermal humification device.

[0181] According to an embodiment of the present invention, a hydrothermal humification product separation device is further provided downstream of the catalytic hydrothermal humification device to separate the gaseous material from the non-gaseous material in the material generated by the catalytic hydrothermal humification device.

[0182] According to an embodiment of the present invention, a hydrothermal humification gaseous material processing device is further provided downstream of the hydrothermal humification product separation device. The hydrothermal humification gaseous material processing device may include a second-phase cooling device and / or a second gaseous purification device, preferably including a second-phase cooling device and a second gaseous purification device.

[0183] According to an embodiment of the present invention, the catalytic hydrothermal humification device may also be provided with at least one hydrothermal humification gas-phase material outlet and at least one solid-liquid-gas mixed material outlet. Preferably, the outlet of the hydrothermal humification gas-phase material of the catalytic hydrothermal humification device is connected to the inlet of the second gas-phase cooling device and / or the second gas-phase purification device of the hydrothermal humification gas-phase treatment device, so as to cool and / or purify the hydrothermal humification gas-phase material.

[0184] According to an embodiment of the present invention, the solid-liquid-gas mixed material outlet of the catalytic hydrothermal humification device is connected to the inlet of the separation device.

[0185] According to an embodiment of the present invention, the catalytic hydrothermal humification product separation device is provided with at least one catalytic hydrothermal humification gas-phase material outlet and at least one hydrothermal humification solid-liquid-gas mixed material outlet. Preferably, the outlet of the catalytic hydrothermal humification gas-phase material is connected to the inlet of the second gas-phase cooling device and / or the second gas-phase purification device, so as to cool and / or purify the gas-phase material of the hydrothermal humification.

[0186] According to an embodiment of the present invention, the condensate obtained by cooling can be mixed with the material provided by the feeding device, for example, it can be mixed with the material provided by the feeding device in the raw material mixer. Therefore, the hydrothermal humification gas-phase treatment device can be connected to the raw material mixer through a liquid-phase conveying pipeline.

[0187] According to an embodiment of the present invention, the gas-phase treatment device can be connected to the discharge device through a gas-phase conveying pipeline, so that the gas obtained after being treated by the hydrothermal humification gas-phase treatment device enters the discharge device for discharge.

[0188] According to an embodiment of the present invention, the solid-liquid-gas mixed material comprises a mixture of solid material, liquid material and gas material.

[0189] According to an embodiment of the present invention, a solid-liquid separation device, such as a centrifuge, is further provided downstream of the hydrothermal humification product separation device. Preferably, the outlet of the hydrothermal humification solid-liquid-gas mixed material is connected to the inlet of the solid-liquid separation device, so as to separate the hydrothermal humification solid-phase material and the hydrothermal humification liquid-phase material in the hydrothermal humification solid-liquid-gas mixed material.

[0190] According to an embodiment of the present invention, the solid-liquid separation device is provided with at least one solid-phase material outlet to provide a solid-phase product.

[0191] According to an embodiment of the present invention, the solid-liquid separation device is provided with at least one liquid-phase material outlet to provide a liquid-phase product.

[0192] According to an embodiment of the present invention, a heavy metal separation device is provided downstream of the solid-liquid separation device. Preferably, the heavy metal separation device can separate heavy metals in the liquid-phase product by physical methods (such as adsorption methods) and / or chemical methods known to those skilled in the art. Therefore, the heavy metal separation device can be a heavy metal physical separation device and / or a heavy metal chemical separation device.

[0193] As an example, an adsorbent or a filtering material, such as an ion exchange resin or a filtering membrane, is provided in the heavy metal separation device to achieve the separation of heavy metals.

[0194] According to an embodiment of the present invention, the temperature of the material entering the catalytic hydrothermal humification device after passing through the buffer separation device is lower than the temperature of the material before entering the buffer separation device.

[0195] According to an embodiment of the present invention, the hydrothermal system is further provided with a heat recovery device to use the heat released by the system to preheat the material provided by the feeding device. For example, the preheating can be achieved by an additional recovery preheater. As an example, the depolymerization device and / or the catalytic hydrothermal humification device can be provided with a heat recovery device. The heat recovery device can be a heat recovery device or a waste heat recovery device known in the art.

[0196] According to an embodiment of the present invention, the hydrothermal system further includes more than one conveying device to convey one, two, or three of the above-mentioned gas-phase materials, solid-phase materials, and gas-phase materials to the corresponding devices in the system for treatment. Preferably, such a conveying device can be provided between every two devices. Those skilled in the art should understand that such a conveying device is known in the art, and therefore the present invention does not particularly limit the specific structure of the conveying device as long as it can effectively convey the material to the desired device.

[0197] According to an embodiment of the present invention, when it is necessary to cool the material, circulating water can be selected for cooling. For this purpose, the cooling device of the present invention can also be provided with a pipeline for circulating cooling water.

[0198] According to an embodiment of the present invention, the temperature for depolymerization of the material containing organic carbon in the depolymerization device can be about 230 - 240 °C, and the depolymerization time can be about 5 - 30 min.

[0199] According to an embodiment of the present invention, the reaction temperature in the catalytic hydrothermal humification device can be about 150 - 230 °C, such as 180 - 200 °C; the reaction time can be about 30 - 300 min, for example 60 - 120 min.

[0200] According to an embodiment of the present invention, the unit 5 may further include one, two or more pre-treatment devices for pre-treating (or "pretreating") the organic carbon-containing material before depolymerization. For example, the pre-treatment includes, but is not limited to, pre-treating the organic carbon-containing material such as pulverizing, pulping, depolymerizing, extracting, soaking, etc.

[0201] According to an embodiment of the present invention, the additive may be an additional additive required for reaction or treatment in any one of the devices in the unit 5, such as one or more of a pH regulator, a catalyst, etc. For example, the additive is an acidic catalyst (such as a solid acidic catalyst or a liquid acidic catalyst), preferably a solid acidic catalyst or an oxygen carrier. As an example, the solid acidic catalyst may be selected from zeolite-based solid acid catalysts, such as zeolite-based solid acid catalytic powdery catalysts or oxygen carriers.

[0202] According to an embodiment of the present invention, the solid acidic catalyst may be the fly ash zeolite-based composite nano oxygen carrier described in Chinese Patent Application No. 202311217726.6.

[0203] According to an embodiment of the present invention, the fly ash is the tiny ash particles discharged during the fuel combustion process, optionally containing or not containing unburned carbonaceous particles, and the fly ash containing unburned carbonaceous particles is also called fly ash or soot. In a preferred embodiment, the fly ash is taken from the combustion fly ash produced by a power plant (including but not limited to the following power plants, such as: coal-fired power plants, biomass power plants, carbon fuel boiler plants, etc.), as well as the fly ash from a fly ash landfill and the ultrafine powder raw material prepared from boiler combustion residues; preferably, the fly ash immediately produced by a power plant pulverized coal boiler is selected. For example, the fly ash collected by the dust collector at the backend of a coal-fired boiler.

[0204] According to an embodiment of the present invention, the oxygen carrier is prepared from fly ash. Preferably, the oxygen carrier is a dual-phase catalytic function oxygen carrier used in novel chemical looping combustion.

[0205] According to an embodiment of the present invention, the solid acid catalyst or oxygen carrier contains a metal oxide and a carrier, for example, the carrier is a fly ash zeolite-based carrier. Preferably, the metal oxide is dispersed in the carrier. For this purpose, a powder form of the metal oxide or a metal oxide containing a dispersant can be used to disperse it in the carrier. For example, in fly ash zeolite-based microporous aluminosilicate crystals, the metal oxide is uniformly distributed (or dispersed) in the crystal structure of the carrier.

[0206] Those skilled in the art should understand that when using a dispersant, the dispersant can be selected from the dispersants known to those skilled in the art as long as it helps to disperse the metal oxide in the carrier.

[0207] According to an embodiment of the present invention, the solid acid catalyst or oxygen carrier is referred to as a primary dispersion in the embodiments of the present invention due to having the above-mentioned dispersed structure.

[0208] According to an embodiment of the present invention, the oxygen carrier has a crystal structure of FAU zeolite.

[0209] According to an embodiment of the present invention, the metal oxide includes but is not limited to oxides of one of the following metals: potassium, sodium, magnesium, iron, zinc, chromium, manganese, cobalt, nickel, copper, aluminum, lead, manganese, zirconium, tin, zinc, tungsten, molybdenum, and vanadium; preferably iron oxide, zinc oxide, and aluminum oxide; as an example, the metal oxide is iron(III) oxide, zinc oxide, and aluminum oxide.

[0210] According to an embodiment of the present invention, when the metal oxide is iron(III) oxide, it may have a nanocrystal particle structure of γ-Fe 2 O 3 、α-Fe 2 O 3 、γ-Fe 3 O 4 .

[0211] According to an embodiment of the present invention, the metal of the metal oxide is derived from the metal contained in the fly ash itself, or an externally added metal or metal oxide. For example, the metal contained in the fly ash itself comes from the metal in the material containing organic carbon.

[0212] According to an embodiment of the present invention, the metal oxide may be nanoparticles. For example, the size of the nanoparticles is 0.1 - 100 nm, such as 1 - 50 nm, and exemplary values are 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50 nm.

[0213] According to an embodiment of the present invention, the metal oxide nanoparticles are iron(III) oxide nanoparticles with a particle size of 3 - 5 nm.

[0214] According to an embodiment of the present invention, the particle shape of the metal oxide can be circular, ellipsoidal, or other regular or irregular shapes.

[0215] According to an embodiment of the present invention, the oxygen carrier is a micro-nano material, that is, it has a micro-nano scale crystal structure.

[0216] According to an embodiment of the present invention, the mass ratio of the metal oxide to the oxygen carrier is 5 - 35 wt%, such as 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%.

[0217] According to an embodiment of the present invention, the particle size of the oxygen carrier is 0.075 mm to 0.2 mm, such as 100 μm, 120 μm, 150 μm, 180 μm.

[0218] According to an embodiment of the present invention, the oxygen carrier is prepared from fly ash as a raw material by an alkali conversion method in a two-stage process of melt polymerization (melt polycondensation)-hydrothermal treatment.

[0219] According to an embodiment of the present invention, the oxygen carrier further comprises one or more metal complexes or non-metal complexes, which are mainly used to modify or promote the catalytic function of metal oxide nanoparticles and / or active metal elements in the oxygen carrier, such as being able to cooperate or compensate with the functions of these metal elements.

[0220] According to an embodiment of the present invention, the metal elements of the metal complexes can be selected from rare earth metal elements and / or metalloid elements; for example, the rare earth metal elements are lanthanum (La) and cerium (Ce) elements, preferably cerium element; for example, the metalloid element is silicon (Si).

[0221] According to an embodiment of the present invention, the metal complexes can also be selected from metal compounds such as ruthenium, nickel, palladium, silver, platinum, nickel, cobalt, vanadium, aluminum, chromium, copper, zinc, molybdenum, tin, manganese, gold, rhodium, zirconium, tungsten, rhenium, osmium, iridium, titanium, etc., preferably compounds of aluminum and zinc, more preferably aluminum oxide and zinc oxide.

[0222] In one embodiment, the rare earth metal elements are derived from their salts or oxides, and the metalloid elements are derived from their oxides (such as silicon dioxide).

[0223] In one embodiment, the metal compound is the corresponding metal salt or oxide.

[0224] According to an embodiment of the present invention, the metal complex is a nanoscale metal oxide, such as nano-ceria, nano-aluminum oxide and / or nano-zinc oxide.

[0225] According to an embodiment of the present invention, the oxygen carrier may further contain additives. For example, the additives are one or more of inorganic acids, inorganic bases, etc. For example, the inorganic acids can be selected from hydrochloric acid, nitric acid, sulfuric acid and / or phosphoric acid, etc., and the inorganic bases can be selected from sodium hydroxide, potassium hydroxide, calcium hydroxide and / or ammonium hydroxide, etc.

[0226] According to an embodiment of the present invention, the solid acid catalyst can be the nano-composite zeolite material described in Chinese Patent Application No. 202310381676.9.

[0227] According to an embodiment of the present invention, the nanoscale crystal structure of the nano-composite zeolite material is a FAU / Zeolite structure, preferably a FAU / Zeolite Y type structure.

[0228] According to an embodiment of the present invention, the nano-composite zeolite material has a micro-mesoporous cage framework void space.

[0229] According to an embodiment of the present invention, the nano-composite zeolite material is an aluminosilicate hydrate.

[0230] According to an embodiment of the present invention, the nano-composite zeolite material further contains one, two or more of the following elements: magnesium (Mg), iron (Fe), zinc (Zn), molybdenum (Mo), boron (B), selenium (Se), etc. Preferably, the element is added to the nano-composite zeolite material as a raw material in the form of its chloride (such as zinc chloride, iron chloride).

[0231] According to an embodiment of the present invention, the nano-composite zeolite material is a faujasite-type structure (FAU).

[0232] According to an embodiment of the present invention, the nano-composite zeolite material has a three-level pore structure: the pore diameter of the first-level pore structure does not exceed 10 nm, such as not exceeding 5 nm, and is preferably less than 2 nm (i.e., micropores); the pore diameter of the second-level pore structure (also called mesopores) is equal to or greater than the pore diameter of the first-level pore structure and does not exceed 50 nm; the pore diameter of the third-level pore structure (also called macropores) is greater than 50 nm, such as greater than 50 nm and not exceeding 500 nm, for example, 200 nm.

[0233] According to an embodiment of the present invention, the sum of the specific surface areas of the nano-composite zeolite material is 150 - 1500 m 2 / g, such as 300 - 1200 m 2 / g, and also such as 500 - 1000 m 2 / g.

[0234] According to an embodiment of the present invention, the cation exchange capacity (CEC, Cation Exchange Capacity) of the nano-composite zeolite material is 150 - 250 cmol(+) / kg.

[0235] According to an embodiment of the present invention, the proportion of the pore volume of the nano-composite zeolite material exceeds 50%, such as exceeding 60%, for example, 65 - 80%.

[0236] According to an embodiment of the present invention, the mass density of the nano-composite zeolite material is 2.1 - 2.2 g / cc.

[0237] According to an embodiment of the present invention, the nano-composite zeolite material has water-holding performance (water retention performance 50 wt%).

[0238] According to an embodiment of the present invention, the nano-composite zeolite material is insoluble in water at any pH. Alternatively, the nano-composite zeolite material has acid and alkali resistance properties, that is, it is insoluble in alkali (high pH) and also insoluble in acid (low pH).

[0239] According to an embodiment of the present invention, the fly ash includes, but is not limited to, one, two or more of the following sources: coal-fired power plants, coal-fired boilers, etc., such as fly ash from fly ash landfills and ultrafine powder raw materials prepared from boiler combustion residues; preferably, fly ash immediately generated from a power plant pulverized coal boiler is selected.

[0240] According to an embodiment of the present invention, each device in the unit 5 is optionally independently provided with a feed port for feeding the additive. Preferably, the organic carbon-containing material after pretreatment is mixed with the additive and then enters the depolymerization device for reaction; or, the organic carbon-containing material after pretreatment and the additive are mixed in the depolymerization reaction device and then react.

[0241] According to an embodiment of the present invention, the additive is a dispersion in which a metal oxide is primarily dispersed in a zeolite-based carrier.

[0242] According to an embodiment of the present invention, the additive is used as a catalyst to catalyze the hydrothermal humification reaction in the catalytic hydrothermal humification device. And preferably, after the hydrothermal humification reaction, the primary dispersion of the zeolite-based additive is further dispersed secondarily in the hydrochar.

[0243] According to an embodiment of the present invention, the weight ratio of the organic carbon-containing material as a raw material to the additive (such as a solid acid catalyst) can be 100:1 to 1:1, such as 10:1 to 2:1, preferably 6:1 to 4:1, more preferably 5:1.

[0244] According to an embodiment of the present invention, preferably, when the weight ratio of the organic carbon-containing material as a raw material to the additive (such as a solid acid catalyst) is 6:1 to 4:1, more preferably 5:1, the reaction temperature of the depolymerization device and / or the catalytic hydrothermal humification device can be reduced to 150 - 180 °C on average, such as 170 °C; and / or, the reaction time of the depolymerization device and / or the catalytic hydrothermal humification device can be reduced to 30 - 120 min, for example 20 - 60 min.

[0245] According to an embodiment of the present invention, the product of the unit 5 includes humin slurry, humic acid composite zeolite-based synthetic material, and humic acid liquid.

[0246] According to an embodiment of the present invention, the product of unit 5 can be processed by a pressure filtration, drying, and / or granulation device to prepare a composition containing modified hydrochar, humic acid, and / or organic carbon medium nutrients, which can be widely used in soil fertilizers, promoting the ecological balance of soil microorganisms and soil animals, promoting the degradation or inactivation of toxic substances in the soil, soil pH improvement, plant fertilizers, promoting plant growth, plant irrigation, etc., and can achieve good effects.

[0247] According to an embodiment of the present invention, unit 5 may further include a storage device for storing the obtained humin slurry, humic acid composite zeolite-based synthetic material, and humic acid liquid product.

[0248] Unit 5 can be modified and adjusted by adding solid acid catalysis in any chemical direction and can also be used to process reaction materials with high and low salt contents simultaneously. The biomass raw material has a significant effect of accelerating humification under the action of solid acid catalytic material. Under solid acid catalytic conditions, humin can be converted into a carbon compound with a sponge-like structure, namely modified hydrochar, whose performance is similar to that of natural humin and can provide the energy and mineral requirements for soil microorganisms and soil animals. The mixture of modified hydrochar and soil humus can more stably or effectively assist in the degradation or inactivation of toxic substances in the soil; the composition of modified hydrochar combined with humus substances and / or organic carbon medium nutrients prepared by unit 5 can buffer the soil pH, release carbon dioxide, and play a role in buffering the hydrogen ion concentration in the soil; and it can be widely used in soil fertilizers, promoting the ecological balance of soil microorganisms and soil animals, promoting the degradation or inactivation of toxic substances in the soil, soil pH improvement, plant fertilizers, promoting plant growth, plant irrigation, etc., and can achieve good effects.

[0249]

Unit 6

[0250] Unit 6 is a C-HTC catalytic hydrothermal carbonization unit for the production of oxygen-carrying carbon-based catalytic combustion aids. The heavy metal-containing raw material is carbonized separately for boiler combustion only.

[0251] Unit 6 is located at the far downstream of the process flow, connecting the discharge ports of unit 5, unit 2', and unit 1; it is the output end of the oxygen-carrying carbon-based catalytic combustion aid.

[0252] The solid acid catalyst can promote the HTC carbonization reaction of biomass and improve the efficiency by 30%; the co-liquid carbonization Co-HTC can improve the combustion quality and cleanliness of the product. The modification of hydrochar by catalytic carbonization can produce a carbon-based raw material with good gasification performance. The dual-phase catalytic function of zeolite-supported metal oxides can catalyze the C-HTC process of this unit 6 to improve the carbonization rate and efficiently produce oxygen-carrying carbon-based catalytic combustion aids.

[0253] According to an embodiment of the present invention, the unit 6 is used for catalytic hydrothermal carbonization (C-HTC).

[0254] According to an embodiment of the present invention, the unit 6 includes a catalytic carbonization device, or includes a depolymerization device and a catalytic carbonization device disposed downstream of the depolymerization device.

[0255] According to an embodiment of the present invention, the catalytic carbonization device is disposed downstream of the depolymerization device, so that the material is processed by the catalytic carbonization device after being processed by the depolymerization device; alternatively, the material can also be directly introduced into the catalytic carbonization device for processing.

[0256] Those skilled in the art should understand that the setting of the catalytic carbonization device downstream of the depolymerization device described herein not only includes the manner of directly processing the material produced by the depolymerization device through the catalytic carbonization device, but also includes the manner of directly introducing the material into the catalytic carbonization device for processing, or the manner of first processing the material produced by the depolymerization device through other devices and then processing it through the catalytic carbonization device. The above different manners should all be understood as alternative manners covered by "the catalytic carbonization device is disposed downstream of the depolymerization device". Therefore, according to an embodiment of the present invention, the depolymerization device and the catalytic carbonization device can be directly connected or not directly connected.

[0257] According to an embodiment of the present invention, a buffer separation device and / or other devices can be provided between the depolymerization device and the catalytic carbonization device downstream thereof. For example, when the depolymerization device and the catalytic carbonization device are not directly connected, the material produced by the depolymerization device can be first processed by the buffer separation device or other devices and then processed by the catalytic carbonization device.

[0258] According to an embodiment of the present invention, the buffer separation device can be a gas-liquid buffer separator, such as a gas-liquid buffer separator known to those skilled in the art.

[0259] According to an embodiment of the present invention, the hydrothermal carbonization system can further include a feeding device to provide a reaction substrate for the depolymerization device. For example, the feeding device is a feeding device for a solid-liquid mixed material (such as 1. humin slurry; 2. solid acid catalytic material; 3. wet biomass homogenate containing municipal sludge; 4. municipal sludge leachate; 5. process medium water circulation; 6. part of the output circulation).

[0260] According to an embodiment of the present invention, the solid-liquid mixed material contains organic carbon.

[0261] According to an embodiment of the present invention, the unit 6 can be used to process materials containing organic carbon, such as humin slurries, or slurries prepared from municipal solid waste (organic solid waste), wet biomass, etc. For example, the materials containing organic carbon can be selected from one, two or more of humin slurries, or materials containing organic carbon such as municipal sludge leachate, municipal solid waste, domestic waste, food waste, kitchen waste, municipal feces, sewage treatment sludge, water bottom sludge, landfill leachate, wood waste residue, crop straws, peat, lignite, bituminous coal, etc. to prepare slurries, or mixtures of slurries.

[0262] For example, when the materials containing organic carbon are selected from raw materials such as domestic waste, food waste, kitchen waste, municipal feces, sewage treatment sludge, water bottom sludge, landfill leachate, wood waste residue, crop straws, etc., they can be pulped first, then depolymerized, and then catalytically carbonized. Alternatively, when the materials containing organic carbon are selected from slurries after pulping such as humin slurries, peat, lignite, bituminous coal, etc., they can be directly catalytically carbonized.

[0263] According to an embodiment of the present invention, the depolymerization device can be provided with at least one feed port for slurries, so that the slurry materials provided by the feeding device enter the depolymerization device.

[0264] According to an embodiment of the present invention, the materials in the feeding device can directly enter the depolymerization device. Or as another option, a raw material mixer, a preheating mixer and / or a mixing storage tank are provided between the feeding device and the depolymerization device, so that the materials in the feeding device enter the depolymerization device after raw material pulping, through the mixer, the preheating mixer and / or the mixing storage tank.

[0265] According to an embodiment of the present invention, the hydrothermal carbonization system can further include a steam generating device to provide the steam required for the depolymerization reaction for the depolymerization device.

[0266] According to an embodiment of the present invention, the steam generating device can also provide the steam required for the carbonization reaction for the catalytic carbonization device.

[0267] According to an embodiment of the present invention, the depolymerization device can be provided with at least one air inlet, so that the steam in the steam generating device enters the depolymerization device.

[0268] According to an embodiment of the present invention, the depolymerization device can also be provided with at least one additive feed port, so that the additives required for the depolymerization reaction enter the depolymerization device.

[0269] Or as another option, the additives can also enter the depolymerization device through the feed port for solid-liquid mixed materials, as long as they can participate in the depolymerization reaction.

[0270] According to an embodiment of the present invention, the depolymerization device may further be provided with at least one depolymerization gas-phase material outlet and at least one depolymerization non-gas-phase material outlet.

[0271] Preferably, the depolymerization gas-phase material includes the tail gas generated by the depolymerization reaction, and the depolymerization non-gas-phase material includes a mixture of solid-phase materials and liquid-phase materials that need to be further processed in a buffer separation device and / or a catalytic carbonization device after being processed by the depolymerization device.

[0272] According to an embodiment of the present invention, the depolymerization gas-phase material outlet of the depolymerization device is connected to the inlet of the depolymerization gas-phase treatment device. The depolymerization gas-phase treatment device may include a first gas-phase cooling device and / or a first gas-phase purification device, preferably including a first gas-phase cooling device and a first gas-phase purification device.

[0273] According to an embodiment of the present invention, the condensate obtained by cooling the depolymerization gas-phase material may be mixed with the material provided by the feeding device, for example, may be mixed with the material provided by the feeding device in a raw material mixer.

[0274] According to an embodiment of the present invention, the depolymerization gas-phase treatment device may be connected to an emission device so that the gas obtained after being processed by the depolymerization gas-phase treatment device enters the emission device for emission.

[0275] According to an embodiment of the present invention, the unit 6 further includes a spiral flow controller to promote the reaction in the depolymerization device and / or the catalytic carbonization device.

[0276] According to an embodiment of the present invention, the depolymerization device and / or the catalytic carbonization device is preferably a horizontal tube reaction device.

[0277] According to an embodiment of the present invention, the catalytic carbonization device is provided with at least one air inlet so that the steam in the steam generation device enters the catalytic carbonization device.

[0278] According to an embodiment of the present invention, a carbonization product separation device is further provided downstream of the catalytic carbonization device to separate the gas-phase material and the non-gas-phase material in the material generated by the catalytic carbonization device.

[0279] According to an embodiment of the present invention, a carbonization gas-phase treatment device is further provided downstream of the carbonization product separation device. The carbonization gas-phase treatment device may include a second gas-phase cooling device and / or a second gas-phase purification device, preferably including a second gas-phase cooling device and a second gas-phase purification device.

[0280] According to an embodiment of the present invention, the catalytic carbonization device may also be provided with at least one carbonized gas-phase material outlet and at least one carbonized solid-liquid-gas mixed material outlet. Preferably, the outlet of the carbonized gas-phase material of the catalytic carbonization device is connected to the inlet of the second gas-phase cooling device and / or the second gas-phase purification device of the carbonized gas-phase treatment device to cool and / or purify the carbonized gas-phase material.

[0281] According to an embodiment of the present invention, the outlet of the carbonized solid-liquid-gas mixed material of the catalytic carbonization device is connected to the inlet of the carbonized product separation device.

[0282] According to an embodiment of the present invention, the carbonized product separation device is provided with at least one carbonized gas-phase material outlet and at least one carbonized solid-liquid-gas mixed material outlet. Preferably, the outlet of the carbonized gas-phase material is connected to the inlet of the second gas-phase cooling device and / or the second gas-phase purification device to cool and / or purify the carbonized gas-phase material.

[0283] According to an embodiment of the present invention, the condensate obtained by cooling the carbonized gas-phase material can be mixed with the material provided by the feeding device, for example, it can be mixed with the material provided by the feeding device in a raw material mixer. Therefore, the carbonized gas-phase treatment device can be connected to the raw material mixer through a liquid-phase conveying pipeline.

[0284] According to an embodiment of the present invention, the carbonized gas-phase treatment device can be connected to the discharging device through a gas-phase conveying pipeline so that the gas obtained after being treated by the carbonized gas-phase treatment device enters the discharging device for discharging.

[0285] According to an embodiment of the present invention, the carbonized solid-liquid-gas mixed material contains a mixture of solid material, liquid material and gas material.

[0286] According to an embodiment of the present invention, a solid-liquid separation device, such as a centrifuge, is further provided downstream of the carbonized product separation device. Preferably, the outlet of the carbonized solid-liquid-gas mixed material is connected to the inlet of the solid-liquid separation device to separate the carbonized solid-phase material and the carbonized liquid-phase material in the carbonized solid-liquid-gas mixed material.

[0287] According to an embodiment of the present invention, the solid-liquid separation device is provided with at least one outlet for carbonized solid-phase material (such as the solid oxygen-carrying carbon-based catalytic combustion aid material and a part of the output cycle) to provide carbonized solid-phase products.

[0288] According to an embodiment of the present invention, the solid-liquid separation device is provided with at least one outlet for carbonized liquid-phase material to provide carbonized liquid-phase products.

[0289] According to an embodiment of the present invention, a heavy metal separation device is provided downstream of the solid-liquid separation device. Preferably, the heavy metal separation device can separate heavy metals in the carbonized liquid phase product by physical methods (such as adsorption methods) and / or chemical methods known to those skilled in the art. Therefore, the heavy metal separation device can be a heavy metal physical separation device and / or a heavy metal chemical separation device.

[0290] As an example, an adsorbent or a filtering material, such as an ion exchange resin or a filtering membrane, is provided in the heavy metal separation device to achieve the separation of heavy metals.

[0291] According to an embodiment of the present invention, the temperature of the material entering the catalytic carbonization device after passing through the buffer separation device is lower than the temperature of the material before entering the buffer separation device.

[0292] According to an embodiment of the present invention, the hydrothermal carbonization system is further provided with a heat recovery device to use the heat released by the system to preheat the material provided by the feeding device. For example, the preheating can be achieved by an additionally provided recovery preheater. As an example, the depolymerization device and / or the catalytic carbonization device can be provided with a heat recovery device. The heat recovery device can be a heat recovery unit or a waste heat recovery unit known in the art.

[0293] According to an embodiment of the present invention, the hydrothermal carbonization system further includes more than one conveying device to convey one, two or three of the above-mentioned gas-phase materials, solid-phase materials, and gas-phase materials to the corresponding devices in the hydrothermal carbonization system for treatment. Preferably, such a conveying device can be provided between every two devices. Those skilled in the art should understand that such a conveying device is known in the art, and therefore the present invention does not particularly limit the specific structure of the conveying device, as long as it can effectively convey the material to the desired device.

[0294] According to an embodiment of the present invention, when it is necessary to cool the material, circulating water can be selected for cooling. For this purpose, the cooling device of the present invention can also be provided with a pipeline for circulating cooling water.

[0295] According to an embodiment of the present invention, the temperature for depolymerizing the organic carbon-containing material in the depolymerization device can be about 230 - 240 °C, and the depolymerization time can be about 5 - 30 min.

[0296] According to an embodiment of the present invention, the reaction temperature in the catalytic carbonization device can be about 150 - 230 °C, such as 180 - 200 °C; the reaction time can be about 30 - 300 min, for example 60 - 120 min.

[0297] According to an embodiment of the present invention, the unit 6 may further include one, two or more pre-treatment devices for pre-treating (or "pretreating") the organic carbon-containing material before depolymerization. For example, the pre-treatment includes, but is not limited to, pre-treating the organic carbon-containing material such as pulverization, pulping, depolymerization, extraction, soaking, etc.

[0298] According to an embodiment of the present invention, the additive may be an additional additive required for reaction or treatment in any one of the devices in the unit 6, such as one or more of a pH regulator, a catalyst, etc. For example, the additive is an acidic catalyst (such as a solid acidic catalyst or a liquid acidic catalyst), preferably a solid acidic catalyst or an oxygen carrier. As an example, the solid acidic catalyst may be selected from zeolite-based solid acid catalysts, such as zeolite-based solid acid catalytic powdery catalysts or oxygen carriers.

[0299] According to an embodiment of the present invention, the solid acidic catalyst may be the fly ash zeolite-based composite nano oxygen carrier described in Chinese Patent Application No. 202311217726.6.

[0300] According to an embodiment of the present invention, the fly ash is the fine ash particles discharged during the fuel combustion process, optionally containing or not containing unburned carbonaceous particles. The fly ash containing unburned carbonaceous particles is also called fly ash or soot. In a preferred embodiment, the fly ash is taken from the combustion fly ash produced by power plants (including, but not limited to, the following power plants, such as coal-fired power plants, biomass power plants, carbon fuel boiler plants, etc.), as well as the fly ash from fly ash landfills and the ultrafine powder raw materials prepared from boiler combustion residues; preferably, the fly ash immediately produced by the pulverized coal boiler of the power plant is selected. For example, the fly ash collected by the dust collector at the back end of the coal-fired boiler.

[0301] According to an embodiment of the present invention, the oxygen carrier is prepared from fly ash. Preferably, the oxygen carrier is an oxygen carrier with a dual-phase catalytic function used in novel chemical looping combustion.

[0302] According to an embodiment of the present invention, the solid acid catalyst or oxygen carrier contains a metal oxide and a carrier, for example, the carrier is a fly ash zeolite-based carrier. Preferably, the metal oxide is dispersed in the carrier. For this purpose, a powder form of the metal oxide or a metal oxide containing a dispersant can be used to disperse it in the carrier. For example, in the fly ash zeolite-based microporous aluminosilicate crystal, the metal oxide is uniformly distributed (or dispersed) in the crystal structure of the carrier.

[0303] Those skilled in the art should understand that when using a dispersant, the dispersant can be selected from the dispersants known to those skilled in the art as long as it helps to disperse the metal oxide in the carrier.

[0304] According to an embodiment of the present invention, the solid acid catalyst or oxygen carrier is referred to as a primary dispersion in the embodiments of the present invention due to having the above-mentioned dispersed structure.

[0305] According to an embodiment of the present invention, the oxygen carrier has a crystal structure of FAU zeolite.

[0306] According to an embodiment of the present invention, the metal oxide includes but is not limited to oxides of one of the metals selected from the following: potassium, sodium, magnesium, iron, zinc, chromium, manganese, cobalt, nickel, copper, aluminum, lead, manganese, zirconium, tin, zinc, tungsten, molybdenum, and vanadium; preferably iron oxide, zinc oxide, and aluminum oxide; as an example, the metal oxide is iron(III) oxide, zinc oxide, and aluminum oxide.

[0307] According to an embodiment of the present invention, when the metal oxide is iron(III) oxide, it may have a nanocrystal particle structure of γ-Fe 2 O 3 、α-Fe 2 O 3 、γ-Fe 3 O 4 .

[0308] According to an embodiment of the present invention, the metal of the metal oxide is derived from the metal contained in the fly ash itself, or an externally added metal or metal oxide. For example, the metal contained in the fly ash itself comes from the metal in the organic carbon-containing material.

[0309] According to an embodiment of the present invention, the metal oxide may be nanoparticles. For example, the size of the nanoparticles is 0.1 - 100 nm, such as 1 - 50 nm, and exemplarily 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50 nm.

[0310] According to an embodiment of the present invention, the metal oxide nanoparticles are iron(III) oxide nanoparticles with a particle size of 3 - 5 nm.

[0311] According to an embodiment of the present invention, the particle shape of the metal oxide may be circular, ellipsoidal, or other regular or irregular shapes.

[0312] According to an embodiment of the present invention, the oxygen carrier is a micro-nano material, that is, it has a micro-nano scale crystal structure.

[0313] According to an embodiment of the present invention, the mass ratio of the metal oxide to the oxygen carrier is 5 - 35 wt%, such as 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%.

[0314] According to an embodiment of the present invention, the particle size of the oxygen carrier is 0.075 mm to 0.2 mm, such as 100 μm, 120 μm, 150 μm, 180 μm.

[0315] According to an embodiment of the present invention, the oxygen carrier is prepared from fly ash as a raw material by an alkali conversion method in a two-stage process of melt polymerization (molten polymerization) - hydrothermal treatment.

[0316] According to an embodiment of the present invention, the oxygen carrier further comprises one or more metal complexes or non-metal complexes, which are mainly used to modify or promote the catalytic function of metal oxide nanoparticles and / or active metal elements in the oxygen carrier, such as being able to cooperate or compensate with the functions of these metal elements.

[0317] According to an embodiment of the present invention, the metal elements of the metal complexes can be selected from rare earth metal elements and / or semi-metal elements; for example, the rare earth metal elements are lanthanum (La) and cerium (Ce) elements, preferably cerium element; for example, the semi-metal element is silicon (Si).

[0318] According to an embodiment of the present invention, the metal complexes can also be selected from metal compounds such as ruthenium, nickel, palladium, silver, platinum, nickel, cobalt, vanadium, aluminum, chromium, copper, zinc, molybdenum, tin, manganese, gold, rhodium, zirconium, tungsten, rhenium, osmium, iridium, titanium, etc., preferably compounds of aluminum and zinc, more preferably aluminum oxide and zinc oxide.

[0319] In one embodiment, the rare earth metal elements are derived from their salts or oxides, and the semi-metal elements are derived from their oxides (such as silicon dioxide).

[0320] In one embodiment, the metal compound is the corresponding metal salt or oxide.

[0321] According to an embodiment of the present invention, the metal complex is a nanoscale metal oxide, such as nano-ceria, nano-aluminum oxide and / or nano-zinc oxide.

[0322] According to an embodiment of the present invention, the oxygen carrier may further contain additives. For example, the additives are one or more of inorganic acids, inorganic bases, etc. For example, the inorganic acids can be selected from hydrochloric acid, nitric acid, sulfuric acid and / or phosphoric acid, etc., and the inorganic bases can be selected from sodium hydroxide, potassium hydroxide, calcium hydroxide and / or ammonium hydroxide, etc.

[0323] According to an embodiment of the present invention, the solid acid catalyst can be the nano-composite zeolite material described in Chinese Patent Application No. 202310381676.9.

[0324] According to an embodiment of the present invention, the nanoscale crystal structure of the nano-composite zeolite material is a FAU / Zeolite structure, preferably a FAU / Zeolite Y type structure.

[0325] According to an embodiment of the present invention, the nano-composite zeolite material has a micro-mesoporous cage framework void space.

[0326] According to an embodiment of the present invention, the nano-composite zeolite material is an aluminosilicate hydrate.

[0327] According to an embodiment of the present invention, the nano-composite zeolite material further contains one, two or more of the following elements: magnesium (Mg), iron (Fe), zinc (Zn), molybdenum (Mo), boron (B), selenium (Se), etc. Preferably, the element is added to the nano-composite zeolite material in the form of its chloride (such as zinc chloride, iron chloride) as a raw material.

[0328] According to an embodiment of the present invention, the nano-composite zeolite material is a faujasite-type structure (FAU).

[0329] According to an embodiment of the present invention, the nano-composite zeolite material has a three-level pore structure: the pore diameter of the first-level pore structure does not exceed 10 nm, such as not exceeding 5 nm, and is preferably less than 2 nm (i.e., micropores); the pore diameter of the second-level pore structure (also called mesopores) is equal to or greater than the pore diameter of the first-level pore structure and does not exceed 50 nm; the pore diameter of the third-level pore structure (also called macropores) is greater than 50 nm, such as greater than 50 nm and not exceeding 500 nm, for example, 200 nm.

[0330] According to an embodiment of the present invention, the sum of the specific surface areas of the nano-composite zeolite material is 150 - 1500 m 2 / g, such as 300 - 1200 m 2 / g, and also such as 500 - 1000 m 2 / g.

[0331] According to an embodiment of the present invention, the cation exchange capacity (CEC, Cation Exchange Capacity) of the nano-composite zeolite material is 150 - 250 cmol(+) / kg.

[0332] According to an embodiment of the present invention, the proportion of the pore volume of the nano-composite zeolite material exceeds 50%, such as exceeding 60%, for example, 65 - 80%.

[0333] According to an embodiment of the present invention, the mass density of the nano-composite zeolite material is 2.1 - 2.2 g / cc.

[0334] According to an embodiment of the present invention, the nano-composite zeolite material has water-holding performance (water retention performance 50 wt%).

[0335] According to an embodiment of the present invention, the nano-composite zeolite material is insoluble in water at any pH. Alternatively, the nano-composite zeolite material has acid and alkali resistance characteristics, that is, it is insoluble in alkali (high pH) and also insoluble in acid (low pH).

[0336] According to an embodiment of the present invention, the fly ash includes, but is not limited to, one, two or more of the following sources: coal-fired power plants, waste incineration plants, boiler combustion sites, etc., such as fly ash from fly ash landfills and ultrafine powder raw materials prepared from boiler combustion residues; preferably, fly ash immediately generated by a power plant pulverized coal boiler is selected.

[0337] According to an embodiment of the present invention, each device in the unit 6 is optionally independently provided with a feed port for feeding the additive. Preferably, the organic carbon-containing material after pre-treatment is mixed with the additive and then enters the depolymerization device for reaction; or, the organic carbon-containing material after pre-treatment and the additive are mixed in the depolymerization reaction device and then react.

[0338] According to an embodiment of the present invention, the additive is a dispersion in which metal oxides are primarily dispersed in a zeolite-based carrier.

[0339] According to an embodiment of the present invention, the additive is used as a catalyst to catalyze the hydrothermal carbonization reaction in the catalytic carbonization device. And preferably, after the hydrothermal carbonization reaction, the primary dispersion of the zeolite-based additive is further dispersed in the hydrochar.

[0340] According to an embodiment of the present invention, the weight ratio of the organic carbon-containing material as a raw material to the additive (such as a solid acid catalyst) can be 100:1 to 1:1, such as 10:1 to 2:1, preferably 6:1 to 4:1, more preferably 5:1.

[0341] According to an embodiment of the present invention, preferably, when the weight ratio of the organic carbon-containing material as a raw material to the additive (such as a solid acid catalyst) is 6:1 to 4:1, more preferably 5:1, the reaction temperature of the depolymerization device and / or the catalytic carbonization device can be reduced to 150 - 180 °C on average, such as 170 °C; and / or, the reaction time of the depolymerization device and / or the catalytic carbonization device can be reduced to 30 - 120 min, for example 20 - 60 min.

[0342] According to an embodiment of the present invention, the product of the unit 6 is a hydrochar slurry of the unit 6 containing the additive (such as a solid acid catalyst, preferably, the content of the solid acid catalyst is higher than 20%).

[0343] According to an embodiment of the present invention, the product can be passed through a pressure filtration, drying, and / or granulation device to prepare a water coke fuel product. Preferably, the particle size of the water coke fuel product can be adjusted to be suitable for the requirements or standards of subsequent units.

[0344] According to an embodiment of the present invention, the unit 6 may further include a storage device for storing the obtained water coke fuel product.

[0345] The unit 6 in the present invention has significant advantages over the currently commonly used HTC process. The co-liquid carbonization method under solid acid catalysis greatly improves the yield, combustion quality, and cleanliness of biomass renewable fuels. The catalytically carbonized modified water coke is also a biomass energy fuel with high cleanliness and good gasification effect.

[0346] The present invention also provides a preparation method of a humic acid composite zeolite-based synthetic material, which is prepared by treating fly ash materials using the above treatment system.

[0347] According to an embodiment of the present invention, the fly ash is the fine ash particles discharged during the fuel combustion process, optionally containing or not containing unburned carbonaceous particles. Fly ash containing unburned carbonaceous particles is also called fly ash or soot. In a preferred embodiment, the fly ash is taken from the combustion fly ash produced by power plants (including but not limited to the following power plants, such as coal-fired power plants, biomass power plants, carbon fuel boiler plants, etc.), as well as fly ash from fly ash landfills and ultrafine powder raw materials prepared from boiler combustion residues; preferably, the fly ash immediately produced by a power plant pulverized coal boiler is selected, preferably the fly ash collected by the dust collector at the rear end of a coal-fired boiler and / or organic waste obtained by pre-cleaning traditional boiler fuels (including low-value lignite, peat, biomass) before combustion.

[0348] According to an embodiment of the present invention, the humic acid composite zeolite-based synthetic material is the product of the above unit 5.

[0349] According to an embodiment of the present invention, in the humic acid composite zeolite-based synthetic material, the mass ratio of humic acid to fly ash zeolite-based material is 1:2 to 10:1, such as 1:1 to 5:1, and exemplary values are 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1.

[0350] According to an embodiment of the present invention, the preparation method of the humic acid composite zeolite-based synthetic material includes the following steps:

[0351] (1) Using fly ash materials as raw materials, prepare additives for use in unit 3 and / or unit 5 and / or unit 6 in unit 1;

[0352] (2) Under the action of the additive prepared in Unit 1, the lignin raw pulp passes through the CAFT humification heterogeneous catalytic Fenton reaction Unit 3 to separate modified lignin similar to humic acid substances (such as Fenton-catalyzed modified lignin pulp);

[0353] (3) The modified lignin produced by Unit 3 is converted into artificial humic acid liquid and humin slurry in Unit 4;

[0354] (4) Under the action of the additive prepared in Unit 1, the humin slurry produced by Unit 4 and the wet biomass homogenate without municipal sludge are subjected to hydrothermal humification in Unit 5 to synthesize artificial humin, humic acid composite zeolite-based synthetic materials and humic acid liquid;

[0355] (5) Under the action of the additive prepared in Unit 1, the artificial humin slurry produced by Unit 5 and the wet biomass homogenate containing municipal sludge are subjected to hydrothermal carbonization in Unit 6 to prepare a solid oxygen-carrying carbon-based catalytic combustion aid material.

[0356] According to the embodiment of the present invention, calculated based on the feed amount of the fly ash material, in the product of Unit 5, the output amount of the humic acid composite zeolite-based synthetic material is 3 to 10 times the feed amount of the fly ash material, preferably 6 times.

[0357] The present invention also provides a method for treating fly ash, including treating fly ash material using the above treatment system.

[0358] The present invention also provides the application of the above treatment system in the preparation of fertilizers (such as slow-release fertilizers).

[0359] The present invention also provides a slow-release fertilizer, containing the above humic acid composite zeolite-based synthetic material, and the nano-composite zeolite material in the humic acid composite zeolite-based synthetic material serves as a carrier for fertilizer active ingredients.

[0360] The humic acid composite zeolite-based material prepared by the treatment system of the present invention can be used as a slow-release fertilizer and can be used as a soil fertility-improving agent to comprehensively enhance soil fertility. According to the application rate of not less than 2.5 metric tons per hectare accumulated over five years, it can reduce the soil ammonia volatilization amount by more than 50%, increase the soil water retention rate by 60% and increase the soil available water storage capacity by 75%.

[0361] The present invention also provides a slow-release herbicide, containing the above humic acid composite zeolite-based material and a herbicide.

[0362] The present invention also provides the applications of the above slow-release fertilizers or slow-release herbicides in fields such as soil and / or planting industry. For example, they can be used as soil fertilizers, to promote the ecological balance of soil microorganisms and soil animals, to promote the degradation or inactivation of toxic substances in the soil, for soil pH improvement, as plant fertilizers, to promote plant growth, for plant irrigation, etc. For example, the leaching fertility of the slow-release fertilizer containing macronutrient cations is at least more than twice that of the same macronutrient chemical cation in terms of stoichiometry.

[0363] According to an embodiment of the present invention, the slow-release fertilizer is used as a soil fertilizer and / or a plant fertilizer.

[0364] The present invention also provides a soil fertilizer, which contains the above humic acid composite zeolite-based material. Among them, the soil fertilizer can be a liquid-solid mixed fertilizer or a solid fertilizer.

[0365] The present invention also provides a preparation method of the above soil fertilizer, which includes preparing from raw materials containing the above humic acid composite zeolite-based material.

[0366] The present invention also provides a soil conditioner, which contains the above humic acid composite zeolite-based material. Among them, the soil conditioner can be a liquid-solid mixed conditioner or a solid conditioner.

[0367] In one embodiment, the soil is sandy soil. For the improvement of sandy soil, after adding the soil conditioner containing the above composite material, the ammonia volatilization amount of the sandy soil can be reduced by 8%, and at the same time, the water retention rate of the sandy soil can be increased by 10% and the available water storage capacity can be increased by 15%.

[0368] In some embodiments, the soil conditioner is used to adjust the physical properties of the soil, such as improving the water holding rate of the soil and reducing the salt content of the soil water.

[0369] In some embodiments, the soil conditioner is used to repair polluted soil. In some soils polluted by heavy metals or radioactive nuclei, composite materials doped with special elements can be applied for the repair of radioactive pollution.

[0370] The present invention also provides a preparation method of the above soil conditioner, which includes preparing from raw materials containing the above humic acid composite zeolite-based material.

[0371] The present invention also provides a plant fertilizer, which contains the above humic acid composite zeolite-based material. Among them, the plant fertilizer can be a liquid-solid mixed fertilizer or a solid fertilizer.

[0372] The present invention also provides a preparation method of the above plant fertilizer, which includes preparing the plant fertilizer from raw materials containing the above humic acid composite zeolite-based material.

[0373] The present invention also provides a plant growth agent containing the above-mentioned humic acid composite zeolite-based material.

[0374] The present invention also provides a preparation method of the above-mentioned plant growth agent, which includes preparing the plant growth agent from a raw material containing the above-mentioned humic acid composite zeolite-based material.

[0375] The present invention also provides the application of the above-mentioned humic acid composite zeolite-based material in wastewater treatment, such as removing ammonia and / or heavy metal ions in wastewater.

[0376] The present invention also provides a wastewater treatment agent containing the above-mentioned humic acid composite zeolite-based material.

[0377] Beneficial effects:

[0378] (1) The present invention uses two kinds of waste materials produced at the front and rear ends of a coal-fired power boiler combustion system as the main raw materials, and synergistically combines the synthesis processes of artificial humic acid and synthetic zeolite; integrates the process of loading beneficial mineral elements and macronutrients. The present invention can realize the large-scale production of a humic acid composite zeolite-based ultra-high-efficiency salt-resistant water-retaining ecological slow-release fertilizer. The high-efficiency slow-release ecological fertilizer of humic acid of the present invention is a composite product of fly ash zeolite-based slow-release material, modified water coke material, humic acid material and / or organic carbon medium material, and a variety of beneficial mineral nutrients, and will be produced on a large scale in the form of solid particles (or powders) or liquid suspension commercial ecological fertilizers. The ecological fertilizer of the present invention can be widely applied in various cultivated land soils (especially various degraded cultivated lands with serious loss of organic carbon), and large-scale long-term application will play a macro effect in promoting the ecological balance of soil microorganisms and soil animals; the treatment system of the present invention uses large coal-fired power enterprises using low-value coal, and takes the (low-value lignite, peat organic components) organic waste substances and fly ash inorganic waste substances produced by them as the resources for recycling, and can realize the low-cost production of humic acid zeolite-based nutrient slow-release fertilizers on an industrial scale.

[0379] (2) The treatment system of the present invention can be applied to the technological transformation of improving the combustion quality of traditional coal-fired boiler systems, that is, using the active organic substances separated from coal fuels as raw materials for producing artificial humic acid, and while realizing the efficient and clean combustion of coal fuels, recycling the organic waste substances harmful to combustion.

[0380] (3) The treatment system of the present invention can be applied to the fly ash collection system of traditional coal-fired boiler systems; the collected fly ash solid waste can be recycled into a high-value (biphasic) solid acid catalytic material, realizing the recycling of various metal elements in fly ash, while improving the thermoelectric conversion efficiency of the unit, recovering beneficial mineral elements, and recycling and feeding back the soil microecology.

[0381] (4) The processing system of the present invention can also utilize wet biomass wastes such as kitchen waste, food waste, organic sludge, and digestate to realize the material and energy values of wet biomass organic carbon renewable resources.

[0382] (5) The present invention coordinates the extraction process of separating the biopolymer components contained in low-calorific lignite with the pretreatment process of cleaning and upgrading the coal combustion raw materials, that is, through the traditional power generation link of cleaning the coal combustion raw materials, on the one hand, it realizes the function of improving the combustion quality of the power plant boiler and the power generation efficiency, and on the other hand, it provides scarce organic raw materials for the HTH process synthesis of artificial humic acid materials. The present invention not only realizes the pretreatment of cleaning and upgrading the coal combustion raw materials for the coal-fired power boiler system, but also coordinates the separation of the bulk raw materials of biopolymers in low-calorific lignite, thus providing favorable conditions for the industrial production of artificial humic acid materials.

[0383] (6) The present invention provides a thermal power plant using fuels such as lignite and peat rich in lignin, and provides a process flow mainly based on the organic waste produced by the pretreatment of its fuel and the inorganic waste of fly ash (fly ash) produced after the boiler combustion and passing through the dust removal device; the process flow of the present invention integrates the synthesis processes of artificial humic acid and synthetic zeolite, couples the loading processes of beneficial mineral elements and macronutrients, and realizes an efficient industrial process of producing humic acid composite zeolite-based ecological slow-release fertilizer products using the waste of coal power plants as the main raw material.

[0384] (7) The fly ash generated during the boiler combustion process is the ash substance after the mineral elements (ash) contained in the above carbon-based fuels are burned at high temperature. The fly ash is similar to volcanic ash in morphology, and the advanced synthesis process of zeolitization can be used to convert the main SiO 2 and Al 2 O 3Element component regeneration, synthesis into high-value synthetic zeolite materials for various uses (molecular sieves, catalysts, adsorbents, etc.). The value of synthetic zeolite lies first in its strong cation exchange capacity, as a highly active cation carrier medium; the cation exchange capacity equivalent to 7.5 tons of synthetic zeolite is equal to the K:O cation equivalent (3.5) of 1 ton (60% KCI) of potassium salt fertilizer. The essence of the international fertilizer market is the market for the demand of the world's modern agricultural planting industry for cation exchange capacity and the supply of cation exchange capacity by the fertilizer production industry. The difference between the synthesis of synthetic zeolite from fly ash solid waste and silica and alumina ore materials is that in the fly ash zeolite-based materials synthesized from the former, a variety of beneficial mineral elements absorbed by plants from ancient times are enriched. Therefore, the fly ash solid waste in the coal power industry actually reserves industrial raw materials for the production of beneficial mineral nutrient fertilizer products in modern agriculture. The mature development of modern zeolitization technology makes the zeolite materials synthesized from fly ash become a unique material containing a variety of alkali metals, transition metals, and various mineral elements beneficial to plant life; because fly ash contains a variety of trace and trace beneficial mineral element oxides, the zeolite synthesized from fly ash has far better value than natural zeolite and other raw material synthetic zeolites in agricultural applications. It can be foreseen that under the environmental non-point source pollution caused by the salt loss of global commercial fertilizers and the pressure of global arable land degradation, the cheap fly ash zeolitized materials, as the controlled-release medium materials for agricultural fertilizers, will be widely used as substitutes for commercial fertilizer salts. The present invention realizes the on-line synthesis of fly ash zeolite materials through Unit 1, and can realize the formulation customization of doped metal oxides, that is, the catalytic performance in various thermochemical specific applications can be realized; that is, the beneficial metal elements in fly ash, through synthesis as components of zeolite-based materials, before finally returning to the land as mineral nutrients, the supported metal oxides can also be recycled as solid acid catalysts to cyclically catalyze and promote the industrial system efficiency of the CAFT, HTH, Co-HTH, Co-HTC processes and the boiler combustion process.

[0385] (8) The present invention, through the Fenton fly ash zeolite-based catalytic reaction in Unit 3, pulps the feed of biomass organic raw materials according to industrial standards; at the same time, excludes heavy metal-containing or inapplicable organic slurries from the processing link of fertilizer intermediates and uses them as additives in the production of catalytic combustion-supporting and oxygen-carrying fuels. Wet biomass refers to plant biomass formed through photosynthesis, including but not limited to biomass wastes formed in the past: agricultural and forestry wastes, agricultural product processing leftovers, livestock and poultry manure, kitchen waste, organic components in peat (peat contains more than 60% lignin), etc.; the residues composed of plants and other biomass are the largest biological renewable resources on the earth (order of magnitude: hundreds of billions of tons / year); only taking a very small part of them for the production of "artificial humic acid" is enough to compensate for the annual loss of global soil organic carbon. Description of the Drawings

[0386] Figure 1 Schematic diagram of the structure of the processing system of the present invention;

[0387] Figure 2 Process flow diagram for the large-scale production of humic acid zeolite-based nutrient slow-release fertilizer by the processing system of the present invention.

[0388] Figure 3 Process flow diagram for the large-scale production of humic acid zeolite-based nutrient slow-release fertilizer by the processing system of the present invention.

[0389] Figure 4 Chemical properties of humic substances;

[0390] Figure 5 Hydrogen-carbon ratio, oxygen-carbon ratio, and fuel calorific value diagrams of lignite, peat, and lignocellulosic substances.

[0391] Figure 6 Process flow diagram of the FA-HTZ fly ash alkali fusion hydrothermal reaction.

[0392] Figure 7 Process flow diagram for the production of humic acid ultra-high efficiency slow-release fertilizer by the collaborative coupling of the processing system of the present invention and a 330,000 kW power production system. Detailed implementation manners

[0393] The following will further elaborate on the present invention in conjunction with the implementation scheme of the production line. It should be understood that the following embodiments are only for illustrative explanation of the present invention and should not be construed as limiting the protection scope of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0394] Example 1

[0395] Refer to Figure 1 , a processing system for humic acid ultra-high efficiency slow-release fertilizer in collaborative coupling with a 330,000 kW power production system, comprising:

[0396] Unit 3 for separating modified lignin of humic acid-like substances;

[0397] Unit 4 located downstream of Unit 3 and for converting the modified lignin of Unit 3 into artificial humic acid;

[0398] Unit 5 located downstream of Unit 4 and for catalyzing hydrothermal humification to synthesize artificial humin;

[0399] Unit 6 located downstream of Unit 5 and for catalyzing hydrothermal carbonization; and

[0400] Unit 1 located upstream of Unit 3 and for preparing additives in Unit 3 and / or Unit 5 and / or Unit 6.

[0401]

Unit 1

[0402] The said Unit 1 is used to prepare additives in Unit 3 and / or Unit 5 and / or Unit 6, for example, to prepare the solid acid catalyst by fly ash alkali melting hydrothermal zeolitization (FA-HTZ).

[0403] The said Unit 1 includes a polymerization reactor, a grinding device, a dilution tank, an ultrasonic device and a hydrothermal activation device connected in sequence.

[0404] The said polymerization reactor is provided with a fly ash inlet and an alkaline reagent inlet.

[0405] The said Unit 1 further includes a filtering device, and the liquid outlet of the filtering device is connected to the dilution tank through a pipeline to recycle the filtered medium liquid.

[0406] The said additive is prepared by an alkali conversion method of melting polymerization-hydrothermal two-stage with fly ash as the raw material.

[0407] The preparation method of the said additive includes the following steps: fly ash is melted and polymerized under alkaline conditions (also known as "alkali fusion"), the obtained polymer is ground, diluted, ultrasonically treated, and subjected to a hydrothermal activation reaction to obtain the oxygen carrier.

[0408] The said alkaline conditions can be provided by strong alkalis, for example, the strong alkalis are potassium hydroxide and / or sodium hydroxide.

[0409] The conditions of the said melting polymerization include: temperature is 400 - 650 °C, time is 2 - 8 h; for example, temperature is 450 - 550 °C, time is 4 - 6 h.

[0410] The said polymer is ground to 0.075 mm - 0.2 mm.

[0411] The concentration of solid substances in the diluted mixture is 1 - 5 mol / L, for example, 2.5 mol / L.

[0412] The diluent used for dilution is water or the liquid medium recovered from the hydrothermal activation reaction.

[0413] Optionally, fly ash is added or not added during dilution.

[0414] The time of the said ultrasonic treatment is 10 - 30 min, for example, 15 min.

[0415] The conditions of the said hydrothermal activation reaction include: temperature is 70 - 100 °C, time is 2 - 8 h; for example, temperature is 80 - 90 °C, time is 4 - 8 h.

[0416] Alternatively, the preparation method of the additive comprises the following steps: the fly ash undergoes a zeolitization process synthesized by two-stage fusion (melting, hydrothermal), and the nano-composite zeolite material is prepared.

[0417] The process of the melting stage comprises: mixing the fly ash with an alkali, heating and melting, grinding, and diluting to obtain a pre-crystallization precursor solution.

[0418] Among them, the alkali is selected from strong alkalis, such as sodium hydroxide.

[0419] Among them, the temperature of the heating and melting can be 500-600 °C, and the time is 1-9 h.

[0420] The process of the hydrothermal stage comprises: an aging and hydrothermal process to obtain crystals; or comprises: adding doping elements, aging and hydrothermal process to obtain crystalline composite element crystals.

[0421] The hydrothermal stage may include a repeated hydrothermal process of adding N doping elements, where N is an integer equal to or greater than 1, such as N = 1, 2, 3, 4, 5, 6, 7, 8, 9, 10.

[0422] Doping elements are added, preferably before the start of the hydrothermal process when N>1, to introduce specified elements and uniformly form highly active catalytic sites.

[0423] The doping elements are introduced through the following dopants, including but not limited to nanoparticles, alkalis, and / or crystal nuclei of the one, two or more doping elements, etc.

[0424] The dopant is added to the pre-crystallization precursor solution, but when N = 1 and N≥2, the preparation of the pre-crystallization precursor solution is different:

[0425] When N = 1, the pre-crystallization precursor solution is obtained by mixing the fly ash with an alkali, or further mixing with a dopant, heating and melting, grinding, and diluting;

[0426] When N≥2, the pre-crystallization precursor solution is obtained by mixing, diluting the filtrate obtained after the completion of the previous hydrothermal crystallization stage, the dopant, and alkali added or not added as required.

[0427] The mass ratio of the dopant to the pre-crystallization precursor solution is 1:(1-5), such as 1:1, 1:2, 1:3, 1:4 or 1:5.

[0428] The temperature of the hydrothermal process is 90-170 °C, and the time is 2-48 h.

[0429] The solid acid catalyst can be the fly ash zeolite-based composite nano-oxygen carrier described in Chinese Patent Application No. 202311217726.6.

[0430] The fly ash is composed of tiny ash particles discharged during the fuel combustion process, optionally containing or not containing unburned carbonaceous particles. Fly ash or soot containing unburned carbonaceous particles is also called. In a preferred embodiment, the fly ash is taken from the combustion fly ash produced by power plants (including but not limited to the following power plants, such as coal-fired power plants, biomass power plants, carbon fuel boiler plants, etc.), as well as fly ash from fly ash landfills and ultrafine powder raw materials prepared from boiler combustion residues; preferably, the fly ash immediately generated by the pulverized coal boiler in the power plant is selected, and preferably the fly ash collected by the dust collector at the back end of the coal-fired boiler.

[0431] The oxygen carrier is prepared from fly ash. Preferably, the oxygen carrier is an oxygen carrier with a dual-phase catalytic function for use in novel chemical looping combustion.

[0432] The oxygen carrier contains a metal oxide and a carrier, where the carrier is a fly ash zeolite-based carrier. Preferably, the metal oxide is dispersed in the carrier. For this purpose, a powder form of the metal oxide or a metal oxide containing a dispersant can be used to disperse it in the carrier. For example, fly ash zeolite-based microporous aluminosilicate crystals, and the metal oxide is uniformly distributed (or dispersed) in the crystal structure of the carrier.

[0433] Those skilled in the art should understand that when using a dispersant, the dispersant can be selected from the dispersants known to those skilled in the art as long as it helps to disperse the metal oxide in the carrier.

[0434] The oxygen carrier has the crystal structure of FAU zeolite.

[0435] The metal oxide includes but is not limited to oxides selected from one of the following metals: potassium, sodium, magnesium, iron, zinc, chromium, manganese, cobalt, nickel, copper, aluminum, lead, manganese, zirconium, tin, zinc, tungsten, molybdenum, and vanadium; preferably iron oxide, zinc oxide, and aluminum oxide; as an example, the metal oxide is iron(III) oxide, zinc oxide, and aluminum oxide.

[0436] When the metal oxide is iron(III) oxide, it can have a nanocrystal particle structure of γ-Fe 2 O 3 、α-Fe 2 O 3 、γ-Fe 3 O 4 .

[0437] The metal of the metal oxide comes from the metal contained in the fly ash itself, or an externally added metal or metal oxide. For example, the metal contained in the fly ash itself comes from the metal in the material containing organic carbon.

[0438] Those skilled in the art should understand that when the processing system is started, metals or metal oxides can be added to the fly ash in Unit 1 as needed to enable the solid acid catalyst to have a sufficient amount of metal oxides. After the processing system is in steady-state operation, when metal elements circulate in the combustion system through oxidation and reduction reactions, there is no need to add additional metals or metal oxides. For this purpose, Unit 3, Unit 4, Unit 5, Unit 6, and Unit 1 of the processing system of the present invention are each enclosed, and the connecting pipelines between Unit 3, Unit 4, Unit 5, Unit 6, and Unit 1 are enclosed to reduce or avoid unnecessary consumption of metal elements.

[0439] The metal oxide can be nanoparticles. For example, the size of the nanoparticles is 0.1 - 100 nm, such as 1 - 50 nm, and exemplarily 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50 nm.

[0440] The metal oxide nanoparticles are iron oxide nanoparticles with a particle size of 3 - 5 nm.

[0441] The particle shape of the metal oxide can be circular, ellipsoidal, or other regular or irregular shapes.

[0442] The oxygen carrier is a micro-nano material, that is, it has a micro-nano crystal structure.

[0443] The mass ratio of the metal oxide to the oxygen carrier is 5 - 35 wt%, such as 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%.

[0444] The particle size of the oxygen carrier is 0.075 mm - 0.2 mm, such as 100 μm, 120 μm, 150 μm, 180 μm.

[0445] The oxygen carrier is prepared from fly ash by an alkali conversion method in a two-stage process of melting polymerization (molten polymerization) - hydrothermal treatment.

[0446] The oxygen carrier also includes one or more metal complexes or non-metal complexes, which are mainly used to modify or promote the catalytic functions of the metal oxide nanoparticles and / or the active metal elements in the oxygen carrier, such as being able to cooperate or compensate with the functions of these metal elements.

[0447] The metal elements of the metal complexes can be selected from rare earth metal elements and / or semi-metal elements; for example, the rare earth metal elements are lanthanum (La) and cerium (Ce) elements, preferably cerium element; for example, the semi-metal element is silicon (Si).

[0448] The metal complex may also be selected from metal compounds such as ruthenium, nickel, palladium, silver, platinum, nickel, cobalt, vanadium, aluminum, chromium, copper, zinc, molybdenum, tin, manganese, gold, rhodium, zirconium, tungsten, rhenium, osmium, iridium, titanium, etc. Preferably, they are compounds of aluminum and zinc, and more preferably, they are aluminum oxide and zinc oxide.

[0449] In one embodiment, the rare earth metal element is derived from its salt or oxide, and the metalloid element is derived from its oxide (such as silicon dioxide).

[0450] In one embodiment, the metal compound is the corresponding metal salt or oxide.

[0451] The metal complex is a nanoscale metal oxide, such as nanoceria, nanoaluminum oxide, and / or nanozinc oxide.

[0452] The size of the metal oxide nanoparticles and / or metal complex is less than 300 nm, preferably less than 200 nm, more preferably less than 100 nm, and still more preferably less than 30 nm, 10 nm, and 4 nm.

[0453] The oxygen carrier may also contain additives. For example, the additives are one or more of inorganic acids, inorganic bases, etc. For instance, the inorganic acid may be selected from hydrochloric acid, nitric acid, sulfuric acid, and / or phosphoric acid, etc., and the inorganic base may be selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, and / or ammonium hydroxide, etc.

[0454] As an example, glycolic acid, as one of the dispersants, helps prevent or at least delay the agglomeration of nanoparticles and the deactivation of the catalyst, and can improve the combustion efficiency.

[0455] The solid acid catalyst may be the nanocomposite zeolite material described in Chinese Patent Application No. 202310381676.9.

[0456] The nanoscale crystal structure of the nanocomposite zeolite material is the FAU / Zeolite structure, preferably the FAU / Zeolite Y type structure.

[0457] The nanocomposite zeolite material has a micro-mesoporous cage-frame void space.

[0458] The nanocomposite zeolite material is a hydrated aluminosilicate.

[0459] The nanocomposite zeolite material further contains one, two, or more of the following elements: magnesium (Mg), iron (Fe), zinc (Zn), molybdenum (Mo), boron (B), selenium (Se), etc. Preferably, the element is added to the nanocomposite zeolite material in the form of its chloride (such as zinc chloride, iron chloride).

[0460] The nano-composite zeolite material has a faujasite-type structure (FAU).

[0461] The nano-composite zeolite material has a three-level pore structure: the pore diameter of the first-level pore structure does not exceed 10 nm, for example, does not exceed 5 nm, and is preferably less than 2 nm (i.e., micropores); the pore diameter of the second-level pore structure (also called mesopores) is equal to or greater than the pore diameter of the first-level pore structure and does not exceed 50 nm; the pore diameter of the third-level pore structure (also called macropores) is greater than 50 nm, for example, greater than 50 nm and does not exceed 500 nm, such as 200 nm.

[0462] The sum of the specific surface areas of the nano-composite zeolite material is 150 - 1500 m 2 / g, for example 300 - 1200 m 2 / g, and also such as 500 - 1000 m 2 / g.

[0463] The cation exchange capacity (CEC, Cation Exchange Capacity) of the nano-composite zeolite material is 150 - 250 cmol(+) / kg.

[0464] The proportion of the pore volume of the nano-composite zeolite material exceeds 50%, for example, exceeds 60%, such as 65 - 80%.

[0465] The mass density of the nano-composite zeolite material is 2.1 - 2.2 g / cc.

[0466] The nano-composite zeolite material has water-holding performance (water retention performance of 50 wt%).

[0467] The nano-composite zeolite material is insoluble in water at any pH. Alternatively, the nano-composite zeolite material has acid and alkali resistance characteristics, that is, it is neither soluble in alkali (high pH) nor soluble in acid (low pH).

[0468] The fly ash includes, but is not limited to, one, two or more of the following sources: combustion fly ash produced by power plants (including but not limited to the following power plants, such as: coal-fired power plants, biomass power plants, carbon fuel boiler plants, etc.), fly ash from fly ash landfills, and ultrafine powder raw materials prepared from boiler combustion residues; preferably, fly ash immediately produced by a power plant pulverized coal boiler is selected, and preferably fly ash collected by a dust collector at the backend of a coal-fired boiler.

[0469] After the hydrothermal activation reaction is completed, the product is filtered, washed, and dried to obtain the additive (such as an oxygen carrier). The solid acid catalyst fly ash zeolite-based material synthesized by Unit 1, as a macronutrient (such as: K + or NH 4 + 、NO3 - A slow-release carrier that can sequentially release nutrient cations in soil water and exchange Na + , Ca 2+ and other cations. The loaded macronutrients only slowly release nutrient cations and exchange and absorb Na + or Ca 2+ in accordance with the inherent preference order of cation exchange in the zeolite structure, reducing soil salinization. The fly ash-synthesized zeolite-based material, with its unique honeycomb-like micro-mesoporous cage structure, dispersedly supports beneficial mineral elements and provides energy and mineral elements for soil microorganisms. When widely used as a fertilizer slow-release medium in soil, it can promote soil microecological balance, promote the degradation or inactivation of soil toxic substances, achieve effects such as promoting plant growth and improving soil.

[0470] The fly ash-synthesized zeolite-based material can also be used as a solid acid catalyst for unit 6, i.e., catalytic hydrothermal carbonization. In the C-HTC liquid-phase reaction of coal fuel pretreatment in unit 5, it can catalyze the carbon conversion rate in the hydrothermal pretreatment process.

[0471]

Unit 2

[0472] In one embodiment of the present invention, the system further includes unit 2 for pulping raw material materials containing lignin such as peat, lignite, and wet biomass.

[0473] Unit 2 is a wet biomass processing and pulping unit for pulping feed raw materials containing lignin components such as peat, lignite, and wet biomass.

[0474] In one embodiment of the present invention, the system further includes an auxiliary pulping processing unit 2' for wet biomass materials that cannot be used as agricultural fertilizers, such as municipal sludge, including organic sludge contaminated with heavy metals.

[0475] In one embodiment of the present invention, unit 2 and unit 2' are located at the feed end of bulk organic materials such as lignite and peat at the upstream of the production process flow to pulp the organic materials containing lignin components according to industrial standards; at the same time, remove the organic slurry containing heavy metals or unsuitable ones from the fertilizer product processing link, and pulp it by the auxiliary pulping processing unit 2' for producing additives for catalytic combustion assistance and oxygen-carrying fuel auxiliary raw materials.

[0476] In one embodiment of the present invention, unit 2 is provided with a feed inlet for peat, lignite, and other raw materials rich in lignocellulose.

[0477] In one embodiment of the present invention, unit 2 is provided with a discharge port for single-water coal slurry.

[0478] In one embodiment of the present invention, the unit 2' is provided with an inlet for feeding municipal sludge or other heavy metal-exceeding organic sludge.

[0479] In one embodiment of the present invention, the unit 2' is provided with an outlet for discharging homogenized municipal sludge.

[0480]

Unit 3

[0481] The unit 3 is used to use additives and the like as catalytic materials for the CAFT (Catalytic Alkli Fenton Treatment) reaction, strengthen the high-density free radical liquid-phase reaction incorporated into lignin particles, and rapidly form an aggregation mode of amphiphilic groups, that is, modified lignin that can separate out humic acid-like substances that can stimulate plants to produce tolerance to salt-induced abiotic stress.

[0482] The unit 3 includes a Fenton reaction slurry preparation device, a microwave device, and an extraction device connected in sequence.

[0483] The Fenton reaction slurry preparation device is provided with a biomass raw material inlet, an additive inlet, and an alkaline reagent inlet.

[0484] The biomass raw material is selected from organic wastes obtained by pre-combustion cleaning treatment of traditional boiler fuels (including low-value lignite, peat, biomass).

[0485] The alkaline reagent can be provided by a strong base. For example, the strong base is potassium hydroxide and / or sodium hydroxide.

[0486] A solid-liquid separation device, such as a centrifuge, is further provided downstream of the microwave device. Preferably, the outlet of the microwave device for mixing materials is connected to the inlet of the solid-liquid separation device so as to separate the solid-phase materials and liquid-phase materials of the Fenton catalytic reaction in the materials mixed by the microwave device.

[0487] The solid-liquid separation device is provided with at least one outlet for the solid-phase materials of the Fenton catalytic reaction to provide solid-phase products of the Fenton catalytic reaction.

[0488] The solid-liquid separation device is provided with at least one outlet for the liquid-phase materials of the Fenton catalytic reaction to provide liquid-phase products of the Fenton catalytic reaction.

[0489] The unit 3 further includes a filtration device. The inlet of the filtration device is connected to the outlet of the extraction device; the liquid outlet of the filtration device is connected to the unit 5 through a pipeline to recycle the water-carbon slurry obtained by filtration.

[0490] The product of the unit 3 is a modified lignin water slurry containing fulvic acid liquid, humic acid liquid, and Fenton slurry, which can stimulate plants to produce tolerance to salt-induced abiotic stress and is similar to humic acid substances.

[0491] The product of the unit 3 can be prepared into a modified lignin aqueous slurry similar to humic acid substances through pressure filtration.

[0492] The unit 3 may further include a storage device for storing the obtained humic acid product.

[0493] The additive is prepared through the unit ○1.

[0494]

Unit 4

[0495] The unit 4 is used to catalyze the hydrothermal humification (HTH) reaction to efficiently convert biomass into artificial humic acid materials.

[0496] The unit 4 includes a catalytic hydrothermal humification device.

[0497] The unit 4 may further include a feeding device to provide a reaction substrate for the catalytic hydrothermal humification device. For example, the feeding device is a feeding device for solid-liquid mixed materials.

[0498] The solid-liquid mixed material contains organic carbon.

[0499] The unit 4 can be used to process materials containing organic carbon, such as the aqueous carbon slurry produced by the unit 3.

[0500] The unit 4 may further include a steam generation device to provide the steam required for the hydrothermal humification reaction for the catalytic hydrothermal humification device.

[0501] The unit 4 further includes a spiral flow controller to promote the reaction in the catalytic hydrothermal humification device.

[0502] The catalytic hydrothermal humification device is preferably a horizontal tube reaction device.

[0503] The catalytic hydrothermal humification device is provided with at least one air inlet so that the steam in the steam generation device enters the catalytic hydrothermal humification device.

[0504] A hydrothermal humification product separation device is further provided downstream of the catalytic hydrothermal humification device to separate the gas-phase material and the non-gas-phase material in the material produced by the catalytic hydrothermal humification device.

[0505] A hydrothermal humification gas-phase treatment device is further provided downstream of the hydrothermal humification product separation device. The hydrothermal humification gas-phase treatment device may include a second gas-phase cooling device and / or a second gas-phase purification device, preferably including a second-phase cooling device and a second gas-phase purification device.

[0506] The catalytic hydrothermal humification device may also be provided with at least one hydrothermal humification gas-phase material outlet and at least one hydrothermal humification solid-liquid-gas mixed material outlet. Preferably, the outlet of the hydrothermal humification gas-phase material of the catalytic hydrothermal humification device is connected to the inlet of the second gas-phase cooling device and / or the second gas-phase purification device of the hydrothermal humification gas-phase treatment device, so as to cool and / or purify the hydrothermal humification gas-phase material.

[0507] The outlet of the hydrothermal humification solid-liquid-gas mixed material of the catalytic hydrothermal humification device is connected to the inlet of the hydrothermal humification product separation device.

[0508] The hydrothermal humification product separation device is provided with at least one hydrothermal humification gas-phase material outlet and at least one hydrothermal humification solid-liquid-gas mixed material outlet. Preferably, the outlet of the hydrothermal humification gas-phase material is connected to the inlet of the second gas-phase cooling device and / or the second gas-phase purification device, so as to cool and / or purify the hydrothermal humification gas-phase material.

[0509] The condensate obtained by cooling the hydrothermal humification gas-phase material can be mixed with the material provided by the feeding device, for example, it can be mixed with the material provided by the feeding device in the raw material mixer. Therefore, the hydrothermal humification gas-phase treatment device can be connected to the raw material mixer through a liquid-phase conveying pipeline.

[0510] The hydrothermal humification gas-phase treatment device can be connected to the discharge device through a gas-phase conveying pipeline, so that the gas obtained after being treated by the hydrothermal humification gas-phase treatment device enters the discharge device for discharge.

[0511] The hydrothermal humification solid-liquid-gas mixed material contains a mixture of solid material, liquid material and gas material.

[0512] A solid-liquid separation device, such as a centrifuge, is further provided downstream of the hydrothermal humification product separation device. Preferably, the outlet of the hydrothermal humification solid-liquid-gas mixed material is connected to the inlet of the solid-liquid separation device, so as to separate the hydrothermal humification solid-phase material and the hydrothermal humification liquid-phase material in the hydrothermal humification solid-liquid-gas mixed material.

[0513] The solid-liquid separation device is provided with at least one hydrothermal humification solid-phase material outlet to provide a hydrothermal humification solid-phase product.

[0514] The solid-liquid separation device is provided with at least one hydrothermal humification liquid-phase material outlet to provide a hydrothermal humification liquid-phase product.

[0515] A heavy metal separation device is provided downstream of the solid-liquid separation device. Preferably, the heavy metal separation device can separate heavy metals in the hydrothermal humification liquid-phase product by physical methods (such as adsorption methods) and / or chemical methods known to those skilled in the art. Therefore, the heavy metal separation device can be a heavy metal physical separation device and / or a heavy metal chemical separation device.

[0516] As an example, an adsorbent or a filtering material, such as an ion exchange resin or a filtering membrane, is provided in the heavy metal separation device to achieve the separation of heavy metals.

[0517] The temperature of the material entering the catalytic hydrothermal humification device through the buffer separation device is lower than the temperature of the material before entering the buffer separation device.

[0518] The unit 4 is further provided with a heat recovery device to use the heat released by the system to preheat the material provided by the feeding device. For example, the preheating can be achieved by an additional recovery preheater. As an example, the catalytic hydrothermal humification device can be provided with a heat recovery device. The heat recovery device can be a heat recovery device or a waste heat recovery device known in the art.

[0519] The unit 4 further includes more than one conveying device to convey one, two or three of the above-mentioned gas-phase materials, solid-phase materials, and gas-phase materials to the corresponding devices of the unit 3 for treatment. Preferably, such a conveying device can be provided between every two devices. Those skilled in the art should understand that such a conveying device is known in the art, and therefore the specific structure of the conveying device is not particularly limited in the present invention as long as it can effectively convey the material to the desired device.

[0520] When it is necessary to cool the material, circulating water can be selected for cooling. For this purpose, the cooling device of the present invention can also be provided with a pipeline for circulating cooling water.

[0521] The reaction temperature in the catalytic hydrothermal humification device can be about 150 - 230 °C, such as 180 - 200 °C; the reaction time can be about 30 - 300 min, for example 60 - 120 min.

[0522] The product of the unit 4 includes humic acid liquid and humin slurry.

[0523] The product of the unit 4 can be processed by a pressure filtration, drying, and / or granulation device to efficiently convert biomass into a humus-like polymer artificial humic acid material.

[0524] The unit 4 can further include a storage device for storing the obtained humin slurry, humic acid composite zeolite-based synthetic material, and humic acid liquid product.

[0525]

Unit 5

[0526] The said Unit 5 is used for catalyzing the catalytic-hydrothermal humification (i.e., C-HTH) reaction to produce humin.

[0527] The said Unit 5 includes a catalytic hydrothermal humification device, or includes a depolymerization device and a catalytic hydrothermal humification device arranged downstream of the depolymerization device.

[0528] The catalytic hydrothermal humification device is arranged downstream of the depolymerization device, so that the material is processed by the catalytic hydrothermal humification device after being processed by the depolymerization device; alternatively, the material can also directly enter the catalytic hydrothermal humification device for processing.

[0529] Those skilled in the art should understand that arranging the catalytic hydrothermal humification device downstream of the depolymerization device as described herein not only includes the way of directly processing the material produced by the depolymerization device through the catalytic hydrothermal humification device, but also includes the way of directly entering the material into the catalytic hydrothermal humification device for processing, or the way of first processing the material produced by the depolymerization device through other devices and then through the catalytic hydrothermal humification device. The above different ways should all be understood as the alternative ways covered by "the catalytic hydrothermal humification device is arranged downstream of the depolymerization device". Therefore, the depolymerization device and the catalytic hydrothermal humification device can be directly connected or not directly connected.

[0530] A buffer separation device and / or other devices can be arranged between the depolymerization device and the catalytic hydrothermal humification device downstream thereof. For example, when the depolymerization device and the catalytic hydrothermal humification device are not directly connected, the material produced by the depolymerization device can be first processed by the buffer separation device or other devices and then by the catalytic hydrothermal humification device.

[0531] The buffer separation device can be a gas-liquid buffer separator, such as the gas-liquid buffer separator known to those skilled in the art.

[0532] The said Unit 5 can also include a feeding device to provide a reaction substrate for the depolymerization device. For example, the feeding device is a feeding device for solid-liquid mixed materials.

[0533] The solid-liquid mixed material contains organic carbon.

[0534] The unit 5 can be used to process organic carbon-containing materials, such as humin slurries, municipal solid waste (organic solid waste), wet biomass, etc. For example, the organic carbon-containing materials can be selected from one, two or more mixtures of humin slurries, wet biomass slurries without municipal sludge, municipal solid waste, domestic waste, food waste, kitchen waste, municipal feces, sewage treatment sludge, water body sediment, landfill leachate, wood waste residue, crop straws, peat, lignite, bituminous coal and other organic carbon-containing materials.

[0535] For example, when the organic carbon-containing materials are selected from domestic waste, food waste, kitchen waste, municipal feces, sewage treatment sludge, water body sediment, landfill leachate, wood waste residue, crop straws, etc., they can be depolymerized first and then catalytically carbonized. Or, when the organic carbon-containing materials are selected from humin slurries, wet biomass slurries without municipal sludge, peat, lignite, bituminous coal, etc., they can be directly catalytically carbonized.

[0536] The depolymerization device can be provided with at least one feed inlet so that the materials provided by the feeding device can enter the depolymerization device.

[0537] The materials in the feeding device can directly enter the depolymerization device. Or as another option, a raw material mixer, a preheating mixer and / or a mixing storage tank are provided between the feeding device and the depolymerization device so that the materials in the feeding device can enter the depolymerization device after passing through the raw material mixer, the preheating mixer and / or the mixing storage tank.

[0538] The unit 5 can also include a steam generating device to provide the steam required for the depolymerization reaction for the depolymerization device.

[0539] The steam generating device can also provide the steam required for the hydrothermal humification reaction for the catalytic hydrothermal humification device.

[0540] The depolymerization device can be provided with at least one steam inlet so that the steam in the steam generating device can enter the depolymerization device.

[0541] The depolymerization device can also be provided with at least one additive feed inlet so that the additives required for the depolymerization reaction can enter the depolymerization device.

[0542] Or as another option, the additives can also enter the depolymerization device through the feed inlet of the solid-liquid mixed materials as long as they can participate in the depolymerization reaction.

[0543] The depolymerization device can also be provided with at least one depolymerization gas-phase material outlet and at least one depolymerization non-gas-phase material outlet.

[0544] Preferably, the depolymerized gaseous material includes the tail gas generated by the depolymerization reaction, and the depolymerized non-gaseous material includes a mixture of solid and liquid materials that need to be further processed in a buffer separation device and / or a catalytic carbonization device after being processed by the depolymerization device.

[0545] The depolymerized gaseous material outlet of the depolymerization device is connected to the inlet of the depolymerized gaseous material processing device. The depolymerized gaseous material processing device may include a first-phase cooling device and / or a first gaseous purification device, preferably including a first-phase cooling device and a first gaseous purification device.

[0546] The condensate obtained by cooling the depolymerized gaseous material can be mixed with the material provided by the feeding device, for example, it can be mixed with the material provided by the feeding device in a raw material mixer.

[0547] The depolymerized gaseous material processing device can be connected to an emission device so that the gas obtained after being processed by the depolymerized gaseous material processing device enters the emission device for emission.

[0548] The unit 5 further includes a spiral flow controller to promote the reaction in the depolymerization device and / or the catalytic hydrothermal humification device.

[0549] The depolymerization device and / or the catalytic hydrothermal humification device is preferably a horizontal tube reaction device.

[0550] The catalytic hydrothermal humification device is provided with at least one air inlet so that the steam in the steam generation device enters the catalytic hydrothermal humification device.

[0551] A hydrothermal humification product separation device is further provided downstream of the catalytic hydrothermal humification device to separate the gaseous material from the non-gaseous material in the material generated by the catalytic hydrothermal humification device.

[0552] A hydrothermal humification gaseous material processing device is further provided downstream of the hydrothermal humification product separation device. The hydrothermal humification gaseous material processing device may include a second-phase cooling device and / or a second gaseous purification device, preferably including a second-phase cooling device and a second gaseous purification device.

[0553] The catalytic hydrothermal humification device may also be provided with at least one hydrothermal humification gaseous material outlet and at least one hydrothermal humification solid-liquid-gas mixed material outlet. Preferably, the outlet of the hydrothermal humification gaseous material of the catalytic hydrothermal humification device is connected to the inlet of the second-phase cooling device and / or the second gaseous purification device of the hydrothermal humification gaseous material processing device to cool and / or purify the hydrothermal humification gaseous material.

[0554] The outlet of the hydrothermal humification solid-liquid-gas mixed material of the catalytic hydrothermal humification device is connected to the inlet of the hydrothermal humification product separation device.

[0555] The hydrothermal humification product separation device is provided with at least one hydrothermal humification gas-phase material outlet and at least one hydrothermal humification solid-liquid-gas mixed material outlet. Preferably, the outlet of the hydrothermal humification gas-phase material is connected to the inlet of the second gas-phase cooling device and / or the second gas-phase purification device to cool and / or purify the hydrothermal humification gas-phase material.

[0556] The condensate obtained by cooling the hydrothermal humification gas-phase material can be mixed with the material provided by the feeding device, for example, it can be mixed with the material provided by the feeding device in the raw material mixer. Therefore, the hydrothermal humification gas-phase treatment device can be connected to the raw material mixer through a liquid-phase conveying pipeline.

[0557] The hydrothermal humification gas-phase treatment device can be connected to the discharging device through a gas-phase conveying pipeline, so that the gas obtained after being treated by the hydrothermal humification gas-phase treatment device enters the discharging device for discharging.

[0558] The hydrothermal humification solid-liquid-gas mixed material contains a mixture of solid material, liquid material and gas material.

[0559] A solid-liquid separation device, such as a centrifuge, is further provided downstream of the hydrothermal humification product separation device. Preferably, the outlet of the hydrothermal humification solid-liquid-gas mixed material is connected to the inlet of the solid-liquid separation device to separate the hydrothermal humification solid-phase material and the hydrothermal humification liquid-phase material in the hydrothermal humification solid-liquid-gas mixed material.

[0560] The solid-liquid separation device is provided with at least one hydrothermal humification solid-phase material outlet to provide a hydrothermal humification solid-phase product.

[0561] The solid-liquid separation device is provided with at least one hydrothermal humification liquid-phase material outlet to provide a hydrothermal humification liquid-phase product.

[0562] A heavy metal separation device is provided downstream of the solid-liquid separation device. Preferably, the heavy metal separation device can separate heavy metals in the hydrothermal humification liquid-phase product by physical methods (such as adsorption method) and / or chemical methods known to those skilled in the art. Therefore, the heavy metal separation device can be a heavy metal physical separation device and / or a heavy metal chemical separation device.

[0563] As an example, an adsorbent or a filtering material, such as an ion exchange resin or a filtering membrane, is provided in the heavy metal separation device to achieve the separation of heavy metals.

[0564] The temperature of the material entering the catalytic hydrothermal humification device through the buffer separation device is lower than the temperature of the material before entering the buffer separation device.

[0565] The hydrothermal humification system is also provided with a heat recovery device to use the heat released by the system for preheating the materials provided by the feeding device. For example, the preheating can be achieved by an additional recovery preheater. As an example, the depolymerization device and / or the catalytic hydrothermal humification device can be provided with a heat recovery device. The heat recovery device can be a heat recovery unit or a waste heat recovery unit known in the art.

[0566] The hydrothermal humification system further includes more than one conveying device to convey one, two or three of the above-mentioned gas-phase materials, solid-phase materials and gas-phase materials to the corresponding devices in the hydrothermal humification system for treatment. Preferably, such a conveying device can be arranged between every two devices. Those skilled in the art should understand that such a conveying device is known in the art. Therefore, the present invention does not particularly limit the specific structure of the conveying device, as long as it can effectively convey the materials to the desired device.

[0567] When it is necessary to cool the materials, circulating water can be selected for cooling. For this purpose, the cooling device of the present invention can also be provided with a pipeline for circulating cooling water.

[0568] The temperature for depolymerizing the organic carbon-containing materials in the depolymerization device can be about 230-240 °C, and the depolymerization time can be about 5-30 min.

[0569] The reaction temperature in the catalytic hydrothermal humification device can be about 150-230 °C, such as 180-200 °C; the reaction time can be about 30-300 min, for example 60-120 min.

[0570] The unit 5 can also include one, two or more pre-treatment devices for pre-treating (or referred to as "pretreating") the organic carbon-containing materials before depolymerization. For example, the pre-treatment includes but is not limited to pre-treating the organic carbon-containing materials such as crushing, pulping, depolymerizing, extracting, soaking, etc.

[0571] The additive can be an additional additive required for the reaction or treatment in any one of the devices in the unit 5, such as one or more of a pH regulator, a catalyst, etc. For example, the additive is prepared through unit ○1.

[0572] Each device in the unit 5 can optionally be independently provided with a feed port for feeding the additive. Preferably, the organic carbon-containing materials after pre-treatment are mixed with the additive and then enter the depolymerization device for reaction; or, the organic carbon-containing materials after pre-treatment are mixed with the additive in the depolymerization reaction device and then react.

[0573] The additive is a dispersion in which a metal oxide is primarily dispersed in a zeolite-based carrier.

[0574] The additive is used as a catalyst for catalyzing the hydrothermal humification reaction in the catalytic hydrothermal humification device. And preferably, after the hydrothermal humification reaction, the primary dispersion of the zeolite-based additive is further secondarily dispersed in the hydrochar.

[0575] The weight ratio of the material containing organic carbon as a raw material to the additive (such as a solid acid catalyst) can be 100:1 to 1:1, such as 10:1 to 2:1, preferably 6:1 to 4:1, more preferably 5:1.

[0576] Preferably, when the weight ratio of the material containing organic carbon as a raw material to the additive (such as a solid acid catalyst) is 6:1 to 4:1, more preferably 5:1, the reaction temperature of the depolymerization device and / or the catalytic hydrothermal humification device can be reduced to 150 - 180 °C on average, such as 170 °C; and / or, the reaction time of the depolymerization device and / or the catalytic hydrothermal humification device can be reduced to 30 - 120 min, for example 20 - 60 min.

[0577] The product of unit 5 includes humin slurry, humic acid composite zeolite-based synthetic material, and humic acid liquid.

[0578] The product of unit 5 can pass through a pressure filtration, drying, and / or granulation device to prepare a composition containing modified hydrochar, humic acid, and / or organic carbon medium nutrients, which can be widely used for soil fertilizers, promoting the ecological balance of soil microorganisms and soil animals, promoting the degradation or inactivation of toxic substances in the soil, soil pH improvement, plant fertilizers, promoting plant growth, plant irrigation, etc., and can achieve good effects.

[0579] Unit 5 may further include a storage device for storing the obtained humin slurry, humic acid composite zeolite-based synthetic material, and humic acid liquid products.

[0580] Unit 5 can be modified and adjusted by solid acid catalyzed addition in any chemical direction, and can also be used to process reaction materials with high salt content and low salt content at the same time. The biomass raw material has a significant effect of accelerating humification under the action of the solid acid catalytic material. Under the condition of solid acid catalysis, humin can be converted into a carbon compound with a sponge-like structure, namely modified hydrochar, whose performance is similar to that of natural humin and can provide the required energy and mineral requirements for soil microorganisms and soil animals. The mixture of modified hydrochar and soil humus can more stably or effectively assist in the degradation or inactivation of toxic substances in the soil; the composition of modified hydrochar combined with humus substances and / or organic carbon medium nutrients prepared by Unit 5 can buffer the soil pH, release carbon dioxide, and play a role in buffering the hydrogen ion concentration in the soil; and it can be widely used in soil fertilizers, promoting the ecological balance of soil microorganisms and soil animals, promoting the degradation or inactivation of toxic substances in the soil, soil pH improvement, plant fertilizers, promoting plant growth, plant irrigation, etc., and can achieve good results.

[0581]

Unit 6

[0582] The said Unit 6 is used for catalytic hydrothermal carbonization (abbreviated as C-HTC).

[0583] The said Unit 6 includes a catalytic carbonization device, or includes a depolymerization device and a catalytic carbonization device arranged downstream of the depolymerization device.

[0584] The catalytic carbonization device is arranged downstream of the depolymerization device so that the material is processed by the catalytic carbonization device after being processed by the depolymerization device; alternatively, the material can also directly enter the catalytic carbonization device for processing.

[0585] As described in this article, arranging the catalytic carbonization device downstream of the depolymerization device not only includes the way of directly processing the material produced by the depolymerization device through the catalytic carbonization device, but also includes the way of directly entering the material into the catalytic carbonization device for processing, or the way of first processing the material produced by the depolymerization device through other devices and then processing it through the catalytic carbonization device. The above different ways should all be understood as the optional ways covered by "the catalytic carbonization device is arranged downstream of the depolymerization device". Therefore, the depolymerization device and the catalytic carbonization device can be directly connected or not directly connected.

[0586] A buffer separation device and / or other devices can be arranged between the depolymerization device and the catalytic carbonization device downstream of it. For example, when the depolymerization device and the catalytic carbonization device are not directly connected, the material produced by the depolymerization device can be first processed by the buffer separation device or other devices and then processed by the catalytic carbonization device.

[0587] The buffer separation device can be a gas-liquid buffer separator, such as a gas-liquid buffer separator known to those skilled in the art.

[0588] The hydrothermal carbonization system may further include a feeding device to provide a reaction substrate for the depolymerization device. For example, the feeding device is a feeding device for a solid-liquid mixed material.

[0589] The solid-liquid mixed material contains organic carbon.

[0590] The unit 6 can be used to process slurries containing organic carbon materials, such as slurries prepared from humin slurries, municipal solid waste (organic solid waste), wet biomass, etc. For example, the organic carbon-containing material can be selected from one, two or more of the slurries of humin slurries, municipal sludge leachate, municipal solid waste, domestic waste, food waste, kitchen waste, municipal feces, sewage treatment sludge, water body sediment, landfill leachate, wood waste residue, crop straw, peat, lignite, bituminous coal and other organic carbon-containing material slurries.

[0591] For example, when the organic carbon-containing material is selected from domestic waste, food waste, kitchen waste, municipal feces, sewage treatment sludge, water body sediment, landfill leachate, wood waste residue, crop straw, etc., it can be pulped, depolymerized first, and then catalytically carbonized. Or, when the organic carbon-containing material is selected from slurries such as humin slurries, peat, lignite, bituminous coal, etc., it can be directly catalytically carbonized.

[0592] The depolymerization device can be provided with at least one feed inlet so that the slurry of the material provided by the feeding device enters the depolymerization device.

[0593] After the material in the feeding device is pulped, it can directly enter the depolymerization device. Or as another option, a mixer for raw material pulping, a preheating mixer and / or a mixing storage tank are provided between the feeding device and the depolymerization device so that the material in the feeding device passes through the raw material mixer, the preheating mixer and / or the mixing storage tank and then enters the depolymerization device.

[0594] The hydrothermal carbonization system may further include a steam generating device to provide steam required for the depolymerization reaction for the depolymerization device.

[0595] The steam generating device can also provide steam required for the carbonization reaction for the catalytic carbonization device.

[0596] The depolymerization device can be provided with at least one steam inlet so that the steam in the steam generating device enters the depolymerization device.

[0597] The depolymerization device can also be provided with at least one additive feed inlet so that the additives required for the depolymerization reaction enter the depolymerization device.

[0598] Alternatively, as another option, the additive can also enter the depolymerization device through the feed port of the solid-liquid mixture, as long as it can participate in the depolymerization reaction.

[0599] The depolymerization device may further be provided with at least one depolymerization gas-phase material outlet and at least one depolymerization non-gas-phase material outlet.

[0600] Preferably, the depolymerization gas-phase material includes the tail gas generated by the depolymerization reaction, and the depolymerization non-gas-phase material includes a mixture of solid-phase material and liquid-phase material that needs to be further processed in the buffer separation device and / or the catalytic carbonization device after being processed by the depolymerization device.

[0601] The depolymerization gas-phase material outlet of the depolymerization device is connected to the inlet of the depolymerization gas-phase treatment device. The depolymerization gas-phase treatment device may include a first gas-phase cooling device and / or a first gas-phase purification device, preferably including a first gas-phase cooling device and a first gas-phase purification device.

[0602] The condensate obtained by cooling the depolymerization gas-phase material can be mixed with the material provided by the feeding device to make a pulp, for example, it can be mixed with the material provided by the feeding device in a raw material mixer to make a pulp.

[0603] The depolymerization gas-phase treatment device may be connected to an emission device so that the gas obtained after being processed by the depolymerization gas-phase treatment device enters the emission device for emission.

[0604] The unit 6 further includes a spiral flow controller to promote the reaction in the depolymerization device and / or the catalytic carbonization device.

[0605] The depolymerization device and / or the catalytic carbonization device is preferably a horizontal tube reaction device.

[0606] The catalytic carbonization device is provided with at least one air inlet so that the steam in the steam generation device enters the catalytic carbonization device.

[0607] A carbonization product separation device is further provided downstream of the catalytic carbonization device to separate the gas-phase material and the non-gas-phase material in the material generated by the catalytic carbonization device.

[0608] A carbonization gas-phase treatment device is further provided downstream of the carbonization product separation device. The carbonization gas-phase treatment device may include a second gas-phase cooling device and / or a second gas-phase purification device, preferably including a second gas-phase cooling device and a second gas-phase purification device.

[0609] The catalytic carbonization device may also be provided with at least one carbonization gas-phase material outlet and at least one carbonization solid-liquid-gas mixed material outlet. Preferably, the outlet of the carbonization gas-phase material of the catalytic carbonization device is connected to the inlet of the second gas-phase cooling device and / or the second gas-phase purification device of the carbonization gas-phase treatment device to cool and / or purify the carbonization gas-phase material.

[0610] The outlet of the carbonization solid-liquid-gas mixed material of the catalytic carbonization device is connected to the inlet of the carbonization product separation device.

[0611] The carbonization product separation device is provided with at least one carbonization gas-phase material outlet and at least one carbonization solid-liquid-gas mixed material outlet. Preferably, the outlet of the carbonization gas-phase material is connected to the inlet of the second gas-phase cooling device and / or the second gas-phase purification device to cool and / or purify the carbonization gas-phase material.

[0612] The condensate obtained by cooling the carbonization gas-phase material can be mixed with the material provided by the feeding device, for example, it can be mixed with the material provided by the feeding device in a raw material mixer. Therefore, the carbonization gas-phase treatment device can be connected to the raw material mixer through a liquid-phase conveying pipeline.

[0613] The carbonization gas-phase treatment device can be connected to the discharging device through a gas-phase conveying pipeline so that the gas obtained after being treated by the carbonization gas-phase treatment device enters the discharging device for discharging.

[0614] The carbonization solid-liquid-gas mixed material contains a mixture of solid material, liquid material and gas material.

[0615] A solid-liquid separation device, such as a centrifuge, is further provided downstream of the carbonization product separation device. Preferably, the outlet of the carbonization solid-liquid-gas mixed material is connected to the inlet of the solid-liquid separation device to separate the carbonization solid-phase material and the carbonization liquid-phase material in the carbonization solid-liquid-gas mixed material.

[0616] The solid-liquid separation device is provided with at least one carbonization solid-phase material outlet to provide a carbonization solid-phase product.

[0617] The solid-liquid separation device is provided with at least one carbonization liquid-phase material outlet to provide a carbonization liquid-phase product.

[0618] A heavy metal separation device is provided downstream of the solid-liquid separation device. Preferably, the heavy metal separation device can separate heavy metals in the carbonization liquid-phase product by physical methods (such as adsorption method) and / or chemical methods known to those skilled in the art. Therefore, the heavy metal separation device can be a heavy metal physical separation device and / or a heavy metal chemical separation device.

[0619] As an example, an adsorbent or a filtering material, such as an ion exchange resin or a filtering membrane, is provided in the heavy metal separation device to achieve the separation of heavy metals.

[0620] The temperature of the material entering the catalytic carbonization device through the buffer separation device is lower than the temperature of the material before entering the buffer separation device.

[0621] The hydrothermal carbonization system is further provided with a heat recovery device to use the heat released by the system to preheat the material provided by the feeding device. For example, the preheating can be achieved by an additional recovery preheater provided. As an example, the depolymerization device and / or the catalytic carbonization device can be provided with a heat recovery device. The heat recovery device can be a heat recovery device or a waste heat recovery device known in the art.

[0622] The hydrothermal carbonization system further includes more than one conveying device to convey one, two or three of the above-mentioned gas-phase material, solid-phase material and gas-phase material to the corresponding devices in the hydrothermal carbonization system for treatment. Preferably, such a conveying device can be provided between every two devices. Those skilled in the art should understand that such a conveying device is known in the art. Therefore, the present invention does not particularly limit the specific structure of the conveying device, as long as it can effectively convey the material to the desired device.

[0623] When it is necessary to cool the material, circulating water can be selected for cooling. For this reason, the cooling device of the present invention can also be provided with a pipeline for circulating cooling water.

[0624] The temperature for depolymerizing the organic carbon-containing material in the depolymerization device can be about 230 - 240 °C, and the depolymerization time can be about 5 - 30 min.

[0625] The reaction temperature in the catalytic carbonization device can be about 150 - 230 °C, such as 180 - 200 °C; the reaction time can be about 30 - 300 min, for example 60 - 120 min.

[0626] The unit 6 can further include one, two or more pre-treatment devices for pre-treating (or referred to as "pretreating") the organic carbon-containing material before depolymerization. For example, the pre-treatment includes but is not limited to pre-treating the organic carbon-containing material such as crushing, pulping, depolymerizing, extracting, soaking, etc.

[0627] The additive can be an additional additive required for the reaction or treatment in any one of the devices in the unit 6, such as one or more of a pH regulator, a catalyst, etc. For example, the additive is prepared through the unit ○1.

[0628] Each device in the unit 6 is optionally independently provided with a feed port for feeding additives. Preferably, the material containing organic carbon after pretreatment is mixed with the additive and then enters the depolymerization device for reaction; alternatively, the material containing organic carbon after pretreatment and the additive are mixed in the depolymerization reaction device and then react.

[0629] The additive is a dispersion in which a metal oxide is primarily dispersed in a zeolite-based carrier.

[0630] The additive is used as a catalyst to catalyze the hydrothermal carbonization reaction in the catalytic carbonization device. And preferably, after the hydrothermal carbonization reaction, the primary dispersion of the zeolite-based additive is further dispersed in the hydrochar.

[0631] The weight ratio of the material containing organic carbon as a raw material to the additive (such as a solid acid catalyst) can be 100:1 to 1:1, such as 10:1 to 2:1, preferably 6:1 to 4:1, and more preferably 5:1.

[0632] Preferably, when the weight ratio of the material containing organic carbon as a raw material to the additive (such as a solid acid catalyst) is 6:1 to 4:1, and more preferably 5:1, the reaction temperature of the depolymerization device and / or the catalytic carbonization device can be reduced to 150 - 180 °C on average, such as 170 °C; and / or the reaction time of the depolymerization device and / or the catalytic carbonization device can be reduced to 30 - 120 min, for example 20 - 60 min.

[0633] The product of the unit 6 is a hydrochar slurry containing the additive (such as a solid acid catalyst, and preferably, the content of the solid acid catalyst is higher than 20%).

[0634] The product of the unit 6 can pass through a filter press, drying, and / or granulation device to prepare a hydrochar fuel product. Preferably, the particle size of the hydrochar fuel product of the unit 6 can be adjusted to meet the requirements or standards of subsequent units.

[0635] It may further include a storage device for storing the obtained hydrochar fuel product.

[0636] The unit 6 in the present invention has significant advantages over the currently commonly used HTC process. The co-liquid carbonization method under solid acid catalysis greatly improves the yield, combustion quality, and cleanliness of biomass renewable fuels. The catalytically carbonized modified hydrochar is also a biomass energy fuel with high cleanliness and good gasification effect.

[0637] Example 2

[0638] Refer to Figure 2, A preparation method of a humic acid composite zeolite-based synthetic material, which is prepared by treating fly ash materials using the treatment system of Example 1, specifically including the following steps:

[0639] (1) Using fly ash materials as raw materials, prepare additives for Unit 3 and / or Unit 5 and / or Unit 6 in Unit 1;

[0640] (2) Under the action of the additives prepared in Unit 1, the lignin raw pulp undergoes a CAFT humification heterogeneous catalytic Fenton reaction in Unit 3 to separate modified lignin similar to humic acid substances (such as Fenton-catalyzed modified lignin pulp);

[0641] (3) The modified lignin produced by Unit 3 is converted into artificial humic acid liquid and humin slurry in Unit 4;

[0642] (4) Under the action of the additives prepared in Unit 1, the humin slurry produced by Unit 4 and the wet biomass homogenate without municipal sludge are subjected to hydrothermal humification in Unit 5 to synthesize artificial humin, humic acid composite zeolite-based synthetic material and humic acid liquid;

[0643] (5) Under the action of the additives prepared in Unit 1, the humin slurry produced by Unit 5 and the wet biomass homogenate containing municipal sludge are subjected to hydrothermal carbonization in Unit 6 to prepare a solid oxygen-carrying carbon-based catalytic combustion aid material.

[0644] The fly ash is the fine ash particles discharged during the fuel combustion process, optionally containing or not containing unburned carbonaceous particles. Fly ash containing unburned carbonaceous particles is also called fly ash or soot. In a preferred embodiment, the fly ash is taken from the combustion fly ash produced by power plants (including but not limited to the following power plants, such as: coal-fired power plants, biomass power plants, carbon fuel boiler plants, etc.), as well as fly ash from fly ash landfills and ultrafine powder raw materials prepared from boiler combustion residues; preferably, the fly ash immediately produced by the power plant pulverized coal boiler is selected, preferably the fly ash collected by the dust collector at the rear end of the coal-fired boiler and / or the organic waste obtained from the pre-combustion cleaning treatment of traditional boiler fuels (including low-value lignite, peat, biomass).

[0645] In the humic acid composite zeolite-based synthetic material, the mass ratio of humic acid to fly ash zeolite-based material is 1:2 to 10:1, such as 1:1 to 5:1, and exemplary values are 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1.

[0646] In this example, the output of the humic acid composite zeolite-based synthetic material in Unit 5 is 3 times the feed amount of the fly ash material.

[0647] Example 3

[0648] A method for treating fly ash, including treating fly ash materials using the treatment system of Example 1.

[0649] Example 4

[0650] A slow-release fertilizer, containing the humic acid composite zeolite-based synthetic material of Example 2, and the nano-composite zeolite material in the humic acid composite zeolite-based synthetic material serves as a carrier for fertilizer active ingredients.

[0651] The humic acid composite zeolite-based material prepared by the treatment system of the above Example 2 can be used as a slow-release fertilizer and can be used as a soil fertility-improving agent to comprehensively enhance soil fertility. Applying the humic acid composite zeolite-based synthetic material of Example 2 at a dosage of not less than 2.5 metric tons per hectare cumulatively over five years can reduce the soil ammonia volatilization by more than 50%, increase the soil water retention rate by 60%, and increase the soil available water storage capacity by 75%.

[0652] Example 5

[0653] Refer to Figure 2 , A preparation method of a humic acid composite zeolite-based synthetic material, which is prepared by using the treatment system of Example 1 to treat fly ash materials, and specifically includes the following steps:

[0654] (1) Using fly ash materials as raw materials, preparing the solid acid catalyst by fly ash alkali fusion hydrothermal zeolitization (FA-HTZ) in Unit 1. The preparation method includes the following steps: Fly ash is fused under alkaline conditions (also known as "alkali fusion"), the obtained polymer is ground, diluted, ultrasonically treated, and then subjected to hydrothermal activation reaction to obtain the solid acid catalyst.

[0655] Alkali fusion conditions: Fly ash and sodium hydroxide are added to the polymerization reactor of Unit 1 through the fly ash inlet and the alkaline reagent inlet respectively according to a mass ratio of 1:1, and after being fully mixed, they are melted. The melting temperature is 600 °C and the time is 2 h. The material enters the grinding device, the polymer is ground to a particle size <0.2 mm, and then enters the dilution tank, where water is added for dilution at a solid substance concentration of 0.10 g / mL. After ultrasonic treatment for 15 min and aging for 12 h, it enters the hydrothermal activation device. At the same time, metal nano-oxides (Fe 2 O 3 , ZnO and Al 2 O 3 are added according to a mass ratio of 1:5 between the dopant and the pre-crystallization solution, where Fe 2 O 3 , ZnO and Al 2 O 3were doped in a mass ratio of 1:1:1), the hydrothermal temperature was 120 °C, and the time was 8 h. After the hydrothermal activation reaction was completed, the product was filtered, washed, and dried to obtain the solid acid catalyst doped with three metal oxides; among them, the content of Fe 2 O 3 was 15.4%, the content of ZnO was 9.2%, and the content of Al 2 O 3 was 14.1%.

[0656] (2) Under the action of the additive solid acid catalyst prepared in Unit 1, the lignin stock solution passed through the CAFT humification heterogeneous catalytic Fenton reaction Unit 3 to separate the modified lignin similar to humic acid substances (such as lignin pulp modified by Fenton catalysis);

[0657] (3) The modified lignin produced in Unit 3 was converted into artificial humic acid liquid and humin slurry in Unit 4;

[0658] (4) Under the action of the additive solid acid catalyst prepared in Unit 1, the humin slurry produced in Unit 4 and the wet biomass homogenate without municipal sludge were hydrothermally humified in Unit 5 to synthesize artificial humin, humic acid composite zeolite-based synthetic materials, and humic acid liquid; Unit 5 includes a depolymerization device and a catalytic hydrothermal humification device arranged downstream of the depolymerization device. Lignite and crop straw were fed into the raw material preheating mixer in a mass ratio of 1:1 and then entered the depolymerization device. At the same time, the solid acid catalyst produced in Unit 1 was added to the depolymerization device at a ratio of 5:1 by weight to the organic carbon-containing material. The depolymerization temperature was 240 °C, and the time was 15 min. After the depolymerization was completed, the slurry entered the catalytic hydrothermal humification device for reaction. The temperature was 180 °C, and the time was 30 min. After solid-liquid separation by a centrifuge, the solid product was granulated to produce the humic acid composite zeolite-based material.

[0659] Calculated based on the feed amount of fly ash material in Unit 1, the output of the humic acid composite zeolite-based synthetic material in the product of Unit 5 was 6 times the feed amount of fly ash material.

[0660] Taking the humic acid composite zeolite-based material prepared in this embodiment as a slow-release fertilizer, applying the humic acid composite zeolite-based material prepared in this embodiment at a rate of not less than 2.5 metric tons per hectare over a cumulative period of five years can reduce the soil ammonia volatilization by more than 50%, increase the soil water retention rate by 60% and increase the soil available water storage capacity by 75%. This shows that: the nano-composite zeolite material synthesized from low-value lignite and fly ash inorganic waste materials produced by large-scale coal-fired power enterprises with low-value coal as the resource target not only has a controllable nano-scale cage-frame slow-release structure, but also contains oxidation phases of various beneficial metal elements evenly distributed from fly ash components transferred to the zeolite matrix. After inheriting trace mineral elements beneficial to plant growth, the zeolite-based material can form artificial humic acid with the same mineral nutrient components as natural humic acid through the composite process with artificial humic acid. Therefore, it can completely replace natural humic acid raw materials to reduce the manufacturing cost of humic acid organic fertilizers. Large-scale application of the ecological fertilizer of the present invention in various cultivated land soils can promote the macroscopic effect of the balance of soil microbial ecology and soil animal ecology.

[0661] The specific embodiments of the present invention have been exemplarily described above through examples. However, the protection scope of the present invention is not limited to the above exemplary embodiments. Any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art within the spirit and principle of the present invention shall be included within the protection scope of the claims of the present invention.

Claims

1. A system comprising: A unit (3) for separating modified lignin from humic acid-like substances; A unit (4) located downstream of the unit (3) and used for converting the modified lignin of the unit (3) into artificial humic acid; A unit (5) located downstream of the unit (4) and used for catalyzing hydrothermal humification to synthesize artificial humin; A unit (6) located downstream of the unit (5) and used for catalytic hydrothermal carbonization; and A unit (1) located upstream of the unit (3) and used for preparing the additives in the unit (3) and / or the unit (5) and / or the unit (6). Preferably, the unit (1) comprises a polymerization reactor, a grinding device, a dilution tank, an ultrasonic device and a hydrothermal activation device connected in sequence. Preferably, the polymerization reactor is provided with a fly ash inlet and an alkaline reagent inlet. Preferably, the unit (1) further comprises a filtering device, the liquid outlet of the filtering device being connected to a dilution tank via a pipeline, so that the medium liquid obtained by filtration can be recovered and reused. Preferably, the additive is prepared by using fly ash as raw material through a fusion-hydrothermal dual-stage alkali conversion method. Preferably, the preparation method of the additive comprises the following steps: melting fly ash under alkaline conditions (also known as "alkali melting"), grinding the obtained polymer, diluting it, ultrasonically treating it, and subjecting it to a hydrothermal activation reaction to obtain the oxygen carrier. Preferably, the preparation method of the additive comprises the following steps: the fly ash is subjected to a two-stage zeolite synthesis process of double-stage fusion (melting and hydrothermal) to prepare the nanocomposite zeolite material. Preferably, the process of the melting stage comprises: mixing fly ash with alkali, heating and melting, grinding, and diluting to obtain a crystallization precursor solution. Preferably, the unit (3) is used to use additives as catalytic materials for the Fenton reaction of the CAFT process, strengthen the high-density free radical liquid phase reaction incorporated into the lignin particles, and quickly form an aggregation pattern of amphiphilic groups, that is, to separate modified lignin similar to humic acid substances that can stimulate plants to produce tolerance to salt-induced abiotic stress. Preferably, the unit (3) comprises a Fenton reaction slurry mixing device, a microwave device and an extraction device connected in sequence. Preferably, the Fenton reaction slurry mixing device is provided with a biomass raw material inlet, an additive inlet and an alkaline reagent inlet. Preferably, the biomass raw material is selected from organic waste that has been cleaned before combustion of traditional boiler fuels (including low-value lignite, peat, and biomass). Preferably, the alkaline agent can be provided by a strong base, for example, the strong base is potassium hydroxide and / or sodium hydroxide. Preferably, a solid-liquid separation device, such as a centrifuge, is further provided downstream of the microwave device. Preferably, the outlet of the mixed material of the microwave device is connected to the inlet of the solid-liquid separation device, so that the solid phase material and the liquid phase material of the Fenton catalytic reaction in the mixed material of the microwave device are separated. Preferably, the solid-liquid separation device is provided with at least one Fenton catalytic reaction solid phase material outlet to provide a Fenton catalytic reaction solid phase product. Preferably, the solid-liquid separation device is provided with at least one Fenton catalytic reaction liquid phase material outlet to provide a Fenton catalytic reaction liquid phase product. Preferably, the unit (3) further comprises a filtering device, the inlet of the filtering device is connected to the outlet of the extraction device; the liquid outlet of the filtering device is connected to the unit (5) via a pipeline, so that the water-carbon slurry obtained by filtration is reused. Preferably, the product of the unit (3) is a modified lignin aqueous slurry comprising fulvic acid liquid, humic acid liquid and Fenton pulp, which is a humic acid-like substance that can stimulate plants to produce tolerance against salt-induced abiotic stress. Preferably, the product of the unit (3) can be filtered by pressure to prepare a modified lignin aqueous slurry similar to a humic acid substance. Preferably, the unit (3) may further comprise a storage device for storing the obtained humic acid product. Preferably, the additive is prepared by unit (1). Preferably, the unit (4) comprises a catalytic hydrothermal humification device. Preferably, the unit (4) may further include a feeding device to provide reaction substrates for the catalytic hydrothermal humification device. For example, the feeding device is a feeding device for a solid-liquid mixture. Preferably, the solid-liquid mixed material contains organic carbon. Preferably, the unit (4) can be used to process organic carbon-containing materials, such as water carbon slurry produced by unit (3). Preferably, the unit (4) may further include a steam generating device to provide the catalytic hydrothermal humification device with steam required for the hydrothermal humification reaction. Preferably, the unit (4) further comprises a spiral flow controller to promote the reaction in the catalytic hydrothermal humification device. Preferably, the catalytic hydrothermal humification device is a horizontal tube reaction device. Preferably, the catalytic hydrothermal humification device is provided with at least one air inlet so that the steam in the steam generating device can enter the catalytic hydrothermal humification device. Preferably, a hydrothermal humification product separation device is further provided downstream of the catalytic hydrothermal humification device to separate gaseous materials from non-gaseous materials in the materials produced by the catalytic hydrothermal humification device. Preferably, a hydrothermal humification gas phase treatment device is further provided downstream of the hydrothermal humification product separation device. The hydrothermal humification gas phase treatment device may include a second gas phase cooling device and / or a second gas phase purification device, preferably including a second phase cooling device and a second gas phase purification device. Preferably, the catalytic hydrothermal humification device may also be provided with at least one hydrothermal humification gas phase material outlet and at least one hydrothermal humification solid-liquid-gas mixture material outlet. Preferably, the outlet of the hydrothermal humification gas phase material of the catalytic hydrothermal humification device is connected to the inlet of the second gas phase cooling device and / or the second gas phase purification device of the hydrothermal humification gas phase treatment device, so as to cool and / or purify the hydrothermal humification gas phase material. Preferably, the outlet of the hydrothermal humification solid-liquid-gas mixture material of the catalytic hydrothermal humification device is connected to the inlet of the hydrothermal humification product separation device. Preferably, the hydrothermal humification product separation device is provided with at least one hydrothermal humification gas phase material outlet and at least one hydrothermal humification solid-liquid-gas mixture material outlet. Preferably, the outlet of the hydrothermal humification gas phase material is connected to the inlet of the second gas phase cooling device and / or the second gas phase purification device to cool and / or purify the hydrothermal humification gas phase material. Preferably, the condensate obtained by cooling the hydrothermal humification gas phase material can be mixed with the material provided by the feeding device, for example, it can be mixed with the material provided by the feeding device in the raw material mixer. Therefore, the hydrothermal humification gas phase treatment device can be connected to the raw material mixer through a liquid phase delivery pipeline. Preferably, the hydrothermal humification gas phase treatment device can be connected to the discharge device through a gas phase conveying pipeline, so that the gas obtained after being treated by the hydrothermal humification gas phase treatment device enters the discharge device for discharge. Preferably, the hydrothermal humification solid-liquid-gas mixture material comprises a mixture of solid material, liquid material and gas material. Preferably, a solid-liquid separation device, such as a centrifuge, is further provided downstream of the hydrothermal humification product separation device. Preferably, the outlet of the hydrothermal humification solid-liquid-gas mixture is connected to the inlet of the solid-liquid separation device, so as to separate the hydrothermal humification solid-phase material and the hydrothermal humification liquid-phase material in the hydrothermal humification solid-liquid-gas mixture. Preferably, the solid-liquid separation device is provided with at least one hydrothermal humification solid phase material outlet to provide a hydrothermal humification solid phase product. Preferably, the solid-liquid separation device is provided with at least one hydrothermal humification liquid phase material outlet to provide a hydrothermal humification liquid phase product. Preferably, a heavy metal separation device is provided downstream of the solid-liquid separation device. Preferably, the heavy metal separation device can separate the heavy metals in the hydrothermal humification liquid phase product by a physical method (such as adsorption method) and / or a chemical method known to those skilled in the art. Therefore, the heavy metal separation device can be a heavy metal physical separation device and / or a heavy metal chemical separation device. Preferably, the heavy metal separation device is provided with an adsorbent or a filter material, such as an ion exchange resin or a filter membrane, to achieve separation of heavy metals. Preferably, the temperature of the material entering the catalytic hydrothermal humification device through the buffer separation device is lower than the temperature of the material before entering the buffer separation device. Preferably, the unit (4) is also provided with a heat recovery device to use the heat released by the system to preheat the material provided by the feeding device. For example, the preheating can be achieved by an additional recovery preheater. As an example, the catalytic hydrothermal humification device can be provided with a heat recovery device. The heat recovery device can be a heat recovery device or a waste heat recovery device known in the art. Preferably, the unit (5) comprises a catalytic hydrothermal humification device, or comprises a depolymerization device and a catalytic hydrothermal humification device arranged downstream of the depolymerization device. Preferably, the unit (6) comprises a catalytic carbonization device, or comprises a depolymerization device and a catalytic carbonization device arranged downstream of the depolymerization device.

2. A method for preparing a humic acid composite zeolite-based synthetic material, which is prepared by treating fly ash materials using the treatment system described in claim 1.

3. A method for treating fly ash, comprising treating fly ash material using the treatment system according to claim 1.

4. A slow-release fertilizer, comprising the humic acid composite zeolite-based synthetic material prepared by the preparation method according to claim 2, wherein the nanocomposite zeolite material in the humic acid composite zeolite-based synthetic material serves as a carrier of the active ingredients of the fertilizer.

5. A slow-release herbicide comprising the zeolite-based slow-release material prepared by the preparation method according to claim 3 and a herbicide.

6. A soil fertilizer, comprising the humic acid composite zeolite-based material prepared by the preparation method according to claim 2. The soil fertilizer can be a liquid-solid mixed fertilizer or a solid fertilizer.

7. A soil conditioner, comprising the humic acid composite zeolite-based material prepared by the preparation method according to claim 2. The soil conditioner can be a liquid-solid mixed conditioner or a solid conditioner.

8. A plant fertilizer comprising the humic acid composite zeolite-based material prepared by the preparation method according to claim 2.

9. A plant growth agent comprising the humic acid composite zeolite-based material prepared by the preparation method according to claim 2.

10. A wastewater treatment agent comprising the zeolite-based adsorption material prepared by the preparation method according to claim 2.

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