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

Abstract

The utility model discloses a production system for synthesizing a humic acid zeolite-based slow-release ecological fertilizer from coal-based organic waste and fly ash waste. The system comprises a first unit, a second unit and a third unit, wherein the first unit is used for separating modified lignin similar to humic acid substances; the second unit is positioned at the downstream of the first unit and is used for converting the modified lignin of the first unit into artificial humic acid; the third unit is positioned at the downstream of the second unit and is used for catalyzing hydrothermal humification synthesis of the artificial humin; the fourth unit is positioned at the downstream of the third unit and is used for catalyzing hydrothermal carbonization; and a fifth unit upstream of the first unit for preparing an additive in the first unit and / or the third unit and / or the fourth unit. According to the utility model, links of feeding pretreatment of main solid waste raw materials of two coal electric boilers, 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 filed with the State Intellectual Property Office of China on November 30, 2023, with patent application number 202311627356.3 and invention name “Production system for synthesizing humic acid zeolite-based slow-release ecological fertilizer from coal-based organic waste and fly ash waste”. The entire text of the prior application is incorporated into this application by reference. Technical Field

[0002] The utility model belongs to a production system for producing agricultural slow-release ecological fertilizers using coal-based organic waste and fly ash waste; it relates to a system integration scheme for the application of fly ash waste and coal-based organic waste regeneration treatment technology and the waste treatment technology in a new production process for synthesizing humic acid zeolite-based slow-release ecological fertilizers; it specifically relates to a production system that integrates industrial wastes of the coal-fired power industry such as coal-fired (low-value lignite, including peat) organic component materials and coal-fired fly ash materials into a new process flow through multiple regeneration technology processing units, so as to achieve efficient and low-cost production of humic acid zeolite-based slow-release ecological fertilizer products. The utility model proposes to use industrial wastes from coal-fired power plants as raw materials for the regeneration of agricultural slow-release fertilizers, which can reduce the cost of producing humic acid organic fertilizer products on a large scale, and by using humic acid zeolite-based ecological fertilizers with slow release of macronutrients to fully replace commercial fertilizers that cause soil non-point source pollution, a variety of macro, micro, and trace beneficial mineral nutrients from plants can be recycled and utilized, and the soil healthy ecology can be fed back in a cycle. Background Art

[0003] The loss and overuse of fertilizers will accelerate the loss of soil organic carbon content and change the pH value of the soil, causing Na + Mg 2+ , Ca 2+ , Cl - 、HCO3 - and SO4 2- The increase in the concentration of various ions such as soil salinity, farmland degradation and the formation of fertilizer salts will have a negative impact on plant growth. The patent application with application number 202311514088.4 discloses a humic acid zeolite-based slow-release fertilizer composed of humic acid organic matter and zeolite inorganic matter. It is a high-efficiency ecological fertilizer that can resist salt and retain water, prevent nutrient loss, and can fully replace commercial fertilizer salts, increase soil organic carbon content, and ensure the long-term activity of soil health.

[0004] Natural zeolite is a scarce mineral resource. Materials with similar natural zeolite structures can be mass-produced using coal fly ash through zeolite technology. The fly ash solid waste produced by most coal-fired power plants in the world (for example, 34% of fly ash in industrial countries around the world) is currently still mainly used for low-value resource applications, such as being used as raw materials for building materials such as cement and ash bricks (including mine backfill, geological stabilization, engineering fillers and road base, etc.). 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, fly ash as an alternative raw material is difficult to compete with traditional mineral materials in terms of cost in building material raw materials. Moreover, as the growth rate of demand for building materials such as cement decreases and the market approaches saturation, the opportunity for fly ash materials to be widely used as a substitute for traditional mineral materials is reduced. As the largest industrial solid waste resource, it is urgently needed to break through the technical bottleneck of its market utilization breadth and high-value regeneration.

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

[0006] The compound of humic acid and zeolite-based slow-release material is a highly efficient ecological fertilizer that can prevent the loss of macronutrients, prevent soil degradation and help plants resist salt stress. However, natural humic acid is an organic nutrient that is generally lacking in cultivated soil. This is because the process of naturally forming humus in the soil is extremely slow, and agricultural 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 and the most abundant on earth is lignocellulose, which is a natural aromatic compound rich in aromatic or aliphatic compounds, derived from the growth of natural plant biomass; it is a three-dimensional, highly cross-linked macromolecular polymer generated by enzyme polymerization, containing a large number of active functional groups such as methoxy, carbonyl, carboxyl and hydroxyl. The emerging HTH process (HydroThermal Humification) can solve the technical difficulties of natural conversion of lignin into humic acid 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, artificial humic acid; according to scientific calculations, the efficiency of synthesizing humic acid organic polymers by HTH process is as high as 10 of the natural process. 9 times.

[0008] Lignin is the main component of peat and low calorific value lignite deposits in the world. The unmineralized biopolymers in lignite are mainly lignin, which will produce a large amount of volatile organic gases (VOC) and water vapor when burned in boilers as fuel, thus reducing the overall benefits of coal-fired power plants. Therefore, raw coal fuels such as lignite and peat, which are rich in biopolymers such as lignin, have the value of large-scale extraction of biopolymers as renewable raw materials for the production of artificial humic acid materials; combining the extraction process of separating the biopolymer components contained in low calorific value lignite with the pretreatment process of clean and quality improvement of lignite raw materials in coal-fired power plants can provide the HTH process with cheap raw materials required for the synthesis of artificial humic acid materials. Utility Model Content

[0009] In order to improve the above-mentioned technical problems, the utility model provides a new production system of humic acid zeolite-based slow-release ecological fertilizer with waste materials such as organic components of coal (low-value lignite, including peat) and fly ash from coal-fired power boilers as the main regeneration raw materials. Specifically, the utility model includes a production system that integrates industrial waste materials in the coal-fired power industry such as organic components of coal (low-value lignite, including peat) and fly ash from coal-fired power boilers into a new process flow through multiple regeneration technology processing units.

[0010] The utility model provides a system, comprising:

[0011] a first unit for separating out modified lignin from humic acid-like substances;

[0012] a second unit located downstream of the first unit and used for converting the modified lignin of the first unit into artificial humic acid;

[0013] A third unit located downstream of the second unit and used for catalyzing hydrothermal humification to synthesize artificial humin;

[0014] a fourth unit located downstream of the third unit and used for catalytic hydrothermal carbonization; and

[0015] A fifth unit is located upstream of the first unit and is used to prepare the additives in the first unit and / or the third unit and / or the fourth unit.

[0016]

Unit 5

[0017] The fifth unit is the FA-HTZ fly ash alkali melting water thermal zeolite process unit, which is used to synthesize the fly ash feedstock of coal-fired power boiler combustion into additives. The additive is a fly ash zeolite-based material (solid acid catalytic material) with functions such as solid acid catalysis, nutrient slow release, and large specific surface area adsorption;

[0018] The fifth unit is located at the feed end of the fly ash solid waste material at the most upstream of the process flow, collects the fly ash material, and synthesizes the fly ash (such as the fly ash in the patent application with application number 202310400924.X) into a compound with a FAU / Zeolite faujasite nanocrystalline structure, i.e., the fly ash zeolite-based material, through the (high-temperature fusion two-stage) hydrothermal zeolite process in the fifth unit. Due to the presence of multiple mineral elements and process-added elements, the output is an additive material for the first unit and / or the third unit and / or the fourth unit with chemically active functions such as solid acid catalysis, cation exchange, and large specific surface area adsorption.

[0019] The main raw materials used for synthesizing the zeolite-based material in the utility model are 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 ultrafine powder raw materials prepared from fly ash from fly ash landfills and boiler combustion residues; preferably, fly ash immediately produced by pulverized coal boilers in power plants is used.

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

[0021] In the utility model, the fly ash zeolite-based material can also be used as the third unit C-HTH and the fourth unit C-HTC, 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 application number 202210886336.7), respectively, to complete the C-HTH catalytic hydrothermal humification of lignin combined with the modification of mineral elements; improve the carbon conversion rate of the C-HTC catalytic hydrothermal carbonization process of biomass.

[0022] According to an embodiment of the present invention, the fifth unit is used to prepare additives in the first unit and / or the third unit and / or the fourth unit, for example, the solid acid catalyst is prepared by a fly ash alkali melting hydrothermal zeolite (FA-HTZ) process.

[0023] According to an embodiment of the present utility model, the fifth unit comprises a fusion reaction furnace, a grinding device, a dilution tank, an ultrasonic device and a hydrothermal activation device which are connected in sequence.

[0024] According to an embodiment of the utility model, the fusion reaction furnace is provided with a fly ash feed inlet, an additive inlet and an alkaline reagent feed inlet.

[0025] According to the implementation scheme of the utility model, the fifth unit further comprises a filtering device, the liquid outlet of the filtering device is connected to the dilution tank through a pipeline, and the medium liquid obtained by filtration is recycled and reused.

[0026] According to the implementation scheme of the utility model, the additive is prepared by using fly ash as raw material through a fusion-hydrothermal dual-stage alkali-melt conversion method.

[0027] According to the embodiment of the utility model, the preparation method of the additive comprises the following steps: melting and agglomerating fly ash under alkaline conditions, grinding and diluting the obtained polymer, ultrasonically treating it, and subjecting it to a hydrothermal activation reaction to obtain the zeolite-based solid acid catalyst.

[0028] 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.

[0029] According to the embodiment of the utility model, the conditions for the smelting include: a temperature of 400-650° C. and a time of 2-8 hours; for example, a temperature of 450-550° C. and a time of 4-6 hours.

[0030] According to an embodiment of the present invention, the polymer is ground to 0.075 mm to 0.2 mm.

[0031] According to an embodiment of the present invention, the concentration of the solid matter in the diluted mixture is 1-5 mol / L, for example, 2.5 mol / L.

[0032] According to the embodiment of the utility model, the diluent used for dilution is water or a liquid medium recovered from a hydrothermal activation reaction.

[0033] According to an embodiment of the present invention, fly ash may or may not be added during dilution.

[0034] According to an embodiment of the present invention, the ultrasonic treatment time is 10-30 min, for example 15 min.

[0035] According to the embodiment of the utility model, the conditions of the hydrothermal activation reaction include: temperature of 70-100° C., time of 2-8 h; for example, temperature of 80-90° C., time of 4-8 h.

[0036] Alternatively, the preparation method of the additive comprises the following steps: the fly ash is subjected to a two-stage synthesis zeolite process of double-stage fusion (melting and hydrothermal) to prepare the nanocomposite zeolite material.

[0037] According to the embodiment of the utility model, the process of the melting stage includes: mixing fly ash with alkali, heating and melting, grinding, and diluting to obtain a crystallization precursor solution.

[0038] Wherein, the base is selected from a strong base, such as sodium hydroxide.

[0039] The heating and melting process may be performed at a temperature of 500 to 600° C. and for a time of 1 to 9 hours.

[0040] According to the implementation scheme of the utility model, the process of the hydrothermal stage includes: aging and hydrothermal process to obtain crystals; or includes: adding doping elements, aging and hydrothermal process to obtain crystallized composite element crystals.

[0041] 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.

[0042] According to the embodiment of the present invention, doping elements are added, preferably before the hydrothermal process with N>1 is started, to introduce designated elements so that these elements uniformly form highly active catalytic sites.

[0043] According to an embodiment of the present invention, the doping element is introduced through the following dopants, including but not limited to nanoparticles, alkaline substances and / or crystal nuclei of the one, two or more doping elements.

[0044] According to the embodiment of the utility model, 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:

[0045] When N=1, the crystal precursor solution is obtained by mixing fly ash with alkali, or further mixing with dopants, heating and melting, grinding, and diluting;

[0046] When N≥2, the crystallization precursor solution is obtained by mixing and diluting the filtrate and dopant obtained after the previous hydrothermal crystallization stage, with or without adding alkali as needed.

[0047] According to an embodiment of the present invention, the mass ratio of the dopant to the crystallization precursor solution is 1:(1-5), for example, 1:1, 1:2, 1:3, 1:4 or 1:5.

[0048] According to the implementation scheme of the utility model, the temperature of the hydrothermal process is 90 to 170° C., and the time is 2 to 48 hours.

[0049] According to an embodiment of the present utility model, the solid acid catalyst may be the fly ash zeolite-based composite nano oxygen carrier described in Chinese patent application No. 202311217726.6.

[0050] According to the implementation scheme of the utility model, the fly ash is a tiny ash particle discharged during the combustion of fuel, which may or may not contain unburned carbonaceous particles, and the unburned carbonaceous particles are also called fly ash or smoke ash. In a preferred embodiment, the fly ash is taken from the combustion fly ash produced by the 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.), and the fly ash from the fly ash landfill and the ultra-fine powder raw material prepared from the boiler combustion residue; preferably, the fly ash generated immediately by the pulverized coal boiler of the power plant is selected, and preferably the fly ash collected by the dust collector at the rear end of the coal-fired boiler is selected.

[0051] According to an embodiment of the present utility model, the oxygen carrier is prepared from fly ash. Preferably, the oxygen carrier is an oxygen carrier with dual-phase catalytic function used in the novel chemical chaining combustion (application number 202311472824.4).

[0052] According to an embodiment of the utility model, the oxygen carrier comprises a metal oxide and a carrier, wherein 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 and add it 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 carrier through a crystallization process.

[0053] It should be understood by those skilled in the art that when a dispersant is used, the dispersant may be selected from dispersants known to those skilled in the art, as long as it helps to disperse the metal oxide in the crystalline precursor solution of the carrier.

[0054] According to an embodiment of the present invention, the solid acid catalyst has a crystal structure of FAU zeolite.

[0055] According to an embodiment of the utility model, the addition of the metal oxide includes but is not limited to oxides of two or more 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, aluminum oxide; as an example, the metal oxide is ferric oxide, zinc oxide, aluminum oxide.

[0056] According to the embodiment of the utility model, when the metal oxide is ferric oxide, it may have a nanocrystalline particle structure of γ-Fe2O3, α-Fe2O3, or γ-Fe3O4.

[0057] According to an embodiment of the utility model, the metal of the metal oxide is derived from the metal contained in the fly ash itself, or an added metal or metal oxide. For example, the metal contained in the fly ash itself is derived from the metal in the material containing organic carbon.

[0058] Those skilled in the art should understand that when the treatment system is started, metal elements, i.e., metal oxides, can be added to the fly ash in unit ○1 as needed so that the solid acid catalyst has a sufficient amount of metal oxides. After the treatment system is in steady-state operation, when the 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, the first unit, the second unit, the third unit, the fourth unit, and the fifth unit of the treatment system of the utility model are each closed, and the connecting pipelines between the first unit, the second unit, the third unit, the fourth unit, and the fifth unit are closed.

[0059] According to an embodiment of the present invention, the metal oxide additive may be nanoparticles. For example, the size of the nanoparticles is 0.1-100 nm, such as 1-50 nm, and exemplified by 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50 nm.

[0060] According to an embodiment of the present invention, the metal oxide nanoparticles are ferric oxide nanoparticles with a particle size of 3-5 nm.

[0061] According to the embodiment of the present invention, the particle shape of the metal oxide can be circular, ellipsoidal or other regular or irregular shapes.

[0062] According to the embodiment of the utility model, the oxygen carrier is a micro-nano material, that is, has a micro-nano crystal structure.

[0063] According to an embodiment of the present utility model, the mass ratio of the metal oxide added to the zeolite-based solid acid catalyst is 5 to 35 wt%, for example, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%.

[0064] According to an embodiment of the present utility model, the particle size of the solid acid catalyst is 0.075 mm to 0.2 mm, for example, 100 μm, 120 μm, 150 μm, 180 μm.

[0065] According to the embodiment of the utility model, the solid acid catalyst or oxygen carrier is prepared from fly ash as raw material through a fusion polymerization (melt polymerization)-hydrothermal two-stage alkali conversion method.

[0066] According to an embodiment of the utility model, the solid acid catalyst or oxygen carrier also includes one or more metal complexes or non-metallic complexes, which are mainly used to modify or promote the catalytic function of the active metal elements in the metal oxide nanoparticles and / or oxygen carriers, such as being able to cooperate with or compensate for the functions of these metal elements.

[0067] According to the embodiment of the utility model, the metal element of the metal complex can be selected from rare earth metal elements and / or semi-metal elements; for example, the rare earth metal element is lanthanum (La) or cerium (Ce), preferably cerium; for example, the semi-metal element is silicon (Si).

[0068] According to the implementation scheme of the present utility model, the metal complex 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, and titanium, preferably compounds of aluminum and zinc, and more preferably aluminum oxide and zinc oxide.

[0069] In one embodiment, the rare earth metal element is derived from its salt or oxide, and the semi-metal element is derived from its oxide (eg, silicon dioxide).

[0070] In one embodiment, the metal compound is the corresponding metal salt or oxide.

[0071] According to an embodiment of the present invention, the metal complex is a nano-scale metal oxide, such as nano-cerium oxide, nano-aluminum oxide and / or nano-zinc oxide.

[0072] 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 further preferably less than 30 nm, 10 nm, or 4 nm.

[0073] According to an embodiment of the present utility model, the solid acid catalyst may be a nanocomposite zeolite material described in Chinese patent application 202310381676.9.

[0074] According to the embodiment of the utility model, the nano-scale crystal structure of the nano-composite zeolite material is a FAU / Zeolite structure, preferably a FAU / Zeolite Y structure.

[0075] According to an embodiment of the present invention, the nanocomposite zeolite material has micro-mesoporous cage void space.

[0076] According to an embodiment of the present utility model, the nanocomposite zeolite material is aluminosilicate hydrate.

[0077] According to an embodiment of the present invention, the nanocomposite zeolite material further comprises one, two or more of the following elements: magnesium (Mg), iron (Fe), zinc (Zn), molybdenum (Mo), boron (B), selenium (Se), etc. Preferably, the elements are added as raw materials to the crystallization precursor solution of the zeolite process in the form of their chlorides (e.g., zinc chloride, iron chloride).

[0078] According to an embodiment of the present invention, the nanocomposite zeolite material is a Fugarst zeolite type structure (FAU).

[0079] According to the implementation scheme of the utility model, the nano-composite zeolite material has a three-level pore structure: the pore diameter of the first-level pore structure does not exceed 10nm, for example, does not exceed 5nm, and is preferably less than 2nm (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 50nm; the pore diameter of the third-level pore structure (also called macropores) is greater than 50nm, for example, greater than 50nm and not more than 500nm, such as 200nm.

[0080] According to the embodiment of the utility model, the sum of the specific surface areas of the nanocomposite zeolite material is 150 to 1500 m 2 / g, for example 300~1200m 2 / g, such as 500~1000m 2 / g.

[0081] According to an embodiment of the present utility model, the cation exchange capacity (CEC) of the nanocomposite zeolite material is 150-250 cmol (+) / kg.

[0082] According to an embodiment of the present invention, the pore volume of the nanocomposite zeolite material accounts for more than 50%, such as more than 60%, such as 65-80%.

[0083] According to an embodiment of the present invention, the mass density of the nanocomposite zeolite material is 2.1-2.2 g / cc.

[0084] According to an embodiment of the present utility model, the nanocomposite zeolite material has water holding performance (water holding performance 50 wt %).

[0085] According to an embodiment of the utility model, the nanocomposite zeolite material is insoluble in water at any pH. Alternatively, the nanocomposite zeolite material has the characteristics of acid and alkali resistance, that is, it is neither soluble in alkali (high pH) nor in acid (low pH).

[0086] According to the implementation scheme of the present utility model, 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.), and ultrafine powder raw materials prepared from fly ash from fly ash landfills and boiler combustion residues; preferably, fly ash generated immediately by pulverized coal boilers in power plants is selected, preferably fly ash collected by dust collectors at the rear end of coal-fired boilers.

[0087] According to the embodiment of the utility model, after the hydrothermal activation reaction is completed, the product is filtered, washed and dried to obtain the additive (such as oxygen carrier). The solid acid catalyst fly ash zeolite-based material synthesized by the fifth unit can also be used as a macronutrient (such as K + or NH4 + 、NO3 - ) is a slow-release carrier that releases nutrient cations and exchanges Na in soil water in sequence. + , Ca 2+ The special function of cations such as zeolite, the macronutrients loaded only follow the inherent preference order of cation exchange of zeolite structure, slowly releasing nutrients, cation exchange and absorbing Na + or Ca 2+, reducing soil salinization; fly ash synthesized zeolite-based materials, with their unique honeycomb micro-mesoporous cage structure, disperse and support beneficial mineral elements, providing energy and mineral elements for soil microorganisms; when widely used in soil as a fertilizer slow-release medium, it can promote soil microecological balance, promote the degradation or inactivation of soil toxic substances, and achieve the effects of promoting plant growth and improving soil.

[0088] The fly ash synthesized zeolite-based material can also be used as the fourth unit, namely the solid acid catalyst for catalytic hydrothermal carbonization; in the C-HTC liquid phase reaction of the fourth unit, it can catalyze the carbon conversion rate of the hydrothermal pretreatment process.

[0089]

Unit 6

[0090] According to an embodiment of the present invention, the system further comprises a sixth unit for pulping raw materials containing lignin such as peat, lignite and wet biomass.

[0091] The sixth unit is a wet biomass processing pulping unit, which is used to pulp feed materials containing lignin components such as peat, lignite and wet biomass.

[0092] According to an embodiment of the utility model, the system further comprises a seventh unit for auxiliary pulping processing of wet biomass materials that cannot be used as agricultural fertilizers, such as municipal sludge and other organic sludges including heavy metal pollution.

[0093] According to the implementation scheme of the utility model, the sixth unit and the seventh unit are located at the feed end of the bulk organic materials such as lignite and peat in the upstream of the production process, so as to pulp the organic materials containing lignin components according to industrial standards; at the same time, the organic pulp containing heavy metals or unsuitable organic pulp is removed from the fertilizer product processing link, and pulped by the auxiliary pulping processing seventh unit for the production of additives for catalytic combustion-supporting and oxygen-carrying fuel auxiliary raw materials.

[0094] In the present invention, the wet biomass used in the sixth unit refers to plant biomass formed by photosynthesis, including but not limited to biomass waste formed in the past: agricultural and forestry waste, agricultural product processing scraps, poultry and livestock feces, kitchen waste, organic components in peat (peat contains more than 60% lignin), etc.; the remains composed of plants and other biomass are the largest biological renewable resources on the earth (the order of magnitude is 100 billion tons / year); a very small part is used to produce "artificial humic acid", which is enough to compensate for the annual loss of global soil organic carbon. Biomass pulping is a traditional process for converting organic materials into industrial raw materials.

[0095] According to an embodiment of the present utility model, the sixth unit is provided with a feed inlet for peat, lignite and other raw materials rich in lignocellulose.

[0096] According to the implementation scheme of the utility model, the sixth unit is provided with a discharge port for the single-water coal slurry.

[0097] According to the implementation scheme of the utility model, the seventh unit is provided with a feed inlet for municipal sludge or other organic sludge containing excessive heavy metals.

[0098] According to the implementation scheme of the utility model, the seventh unit is provided with a discharge port for the municipal sludge homogenate.

[0099]

Unit 1

[0100] The first unit is the CAFT (Catalytic Alkali Fenton Treatment) alkaline liquid Fenton catalytic modification unit, which is used to convert bulk raw materials such as peat and lignite into lignin slurry, separate amphiphilic group aggregates and fulvic acid liquid through heterogeneous Fenton reaction of lignin humification, and produce Fenton catalytically modified lignin alkaline slurry.

[0101] The first unit is located downstream of the discharge end of the solid acid catalytic material of the fifth unit and downstream of the discharge end of the water-coal slurry. It is used to mix the zeolite-based solid acid catalytic material from the fifth unit into the lignin particles of the coal slurry, and mix it with the additive feed H2O2 of the first unit, alkaline reagents such as NaOH to react with high-density free radicals, quickly strengthen the aggregation mode of the amphiphilic group, that is, to separate the modified lignin precipitate of humic acid-like substances that can stimulate plants to produce tolerance to salt-induced abiotic stress. Various beneficial mineral elements such as iron oxide from the fifth unit on a zeolite basis are doped and deposited in the separated lignin polymer and zeolite crystal mixed precipitate, promoting the composite precipitation of lignin particles and zeolite crystal doped 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.

[0102] The water storage performance of the soil humic acid material structure may be destroyed at any time due to water loss, but the zeolite structure with a water content of 50wt% 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 reversible and stable water storage structure.

[0103] According to the implementation scheme of the utility model, the first unit is used to use the fly ash zeolite-based solid acid catalyst prepared in the fifth unit as a catalytic material for the Fenton reaction, to strengthen the liquid phase reaction of high-density free radicals incorporated into the lignin particles, and to 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.

[0104] According to an embodiment of the present utility model, the first unit comprises a Fenton reaction slurry mixing device, a microwave device and an extraction device which are connected in sequence.

[0105] According to the implementation scheme of the utility model, the Fenton reaction slurry mixing device is provided with a biomass raw material inlet, an additive (solid acid catalytic material) inlet and an alkaline reagent inlet.

[0106] According to the implementation scheme of the utility model, 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).

[0107] According to an embodiment of the present invention, the alkaline agent can be provided by a solution of a strong base combined with H2O2, and the strong base is potassium hydroxide and / or sodium hydroxide.

[0108] According to an embodiment of the utility model, 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.

[0109] According to the implementation scheme of the utility model, 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.

[0110] According to the implementation scheme of the utility model, 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.

[0111] According to the implementation scheme of the utility model, the first unit also includes 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 third unit through a pipeline, and the water-carbon slurry obtained by filtration is reused.

[0112] According to an embodiment of the utility model, the product of the first unit is a Fenton-catalyzed modified lignin slurry comprising fulvic acid liquid, humic acid liquid and humic acid-like substances that can stimulate plants to produce tolerance to salt-induced abiotic stress.

[0113] According to an embodiment of the present invention, the product of the first unit can be filtered by pressure to prepare a modified lignin slurry similar to a humic acid substance.

[0114] According to an embodiment of the present invention, the first unit may further include a storage device for storing the obtained humic acid product.

[0115] According to an embodiment of the utility model, the additive is prepared by using fly ash as raw material through a fusion-hydrothermal dual-stage alkali conversion method. Exemplarily, the additive is prepared by the fifth unit.

[0116] The first unit Fenton fly ash zeolite-based catalytic reaction designed by the utility model uses the fifth unit zeolite-based material synthesized from fly ash as a catalyst, including but not limited to the addition of iron oxide zeolite-based materials and the like deposited in a separated lignin matrix, and lignin particles modified by the Fenton reaction promoted by the zeolite-based material; beneficial mineral elements are doped, and in a soil formation environment similar to natural humic acid, the lignin is separated and compositely precipitated with zeolite-based cage pore structure crystal particles containing a variety of beneficial mineral elements.

[0117] Zeolite-based materials have a highly chemically stable cage 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 hydrate crystal structure material of aluminosilicate, its 50wt% water-retaining buffer structure is also permanent. Because the effect of drought on the water-retaining structure of soil humic acid substances is irreversible, that is, the water-storage buffer structure of humic acid substances can be destroyed at any time due to water loss, but the permanent combination with zeolite-based materials can "complement" the water retention in the soil, and can synergistically enhance the water-holding capacity of the composite material, and still retain a reversible water storage buffer after drought water loss.

[0118]

Unit 2

[0119] The second unit is the HTH artificial humic acid process synthesis unit, which is used for the alkaline solution hydrothermal humification reaction process to synthesize artificial humic acid, and simultaneously completes the synthesis of artificial humic acid from lignin and the separation of humin.

[0120] The second unit is located downstream of the unit discharge port, and converts biomass into artificial humic acid material through "Hydrothermal Humification (HTH)".

[0121] Natural humic acid is a product of biomass degradation through natural biological, physical and chemical processes. Lignin can be converted into a polymer similar to humus through the copolymerization reaction of the HTH process. The polymer combines with soil minerals to form a soil humic acid complex, which can obtain stability for thousands of years. The solid acid catalytic material produced by the fifth unit contains elements similar to soil minerals. It is mixed with the Fenton-catalyzed modified lignin slurry produced by the first unit and enters the HTH device of the second unit to provide a variety of beneficial mineral elements required to complete the copolymerization reaction of lignin and the modification of molecular composition. After the HTH of the second unit, the lignin is converted into a polymer with ion exchange activity similar to that of natural humic acid.

[0122] According to the embodiment of the utility model, the second unit is used for hydrothermal humification (HTH) reaction, and biomass can be efficiently converted into artificial humic acid material.

[0123] According to an embodiment of the utility model, the second unit 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 a solid-liquid mixture. Exemplarily, the Fenton-catalyzed modified lignin pulp of the first unit enters the second unit through the feeding device.

[0124] According to an embodiment of the present invention, the second unit can be used to process materials containing organic carbon, such as Fenton-catalyzed modified lignin slurry organic materials produced by the first unit.

[0125] According to an embodiment of the present invention, the second unit may further include a steam generating device to provide the hydrothermal humification device with steam required for the hydrothermal humification reaction.

[0126] According to an embodiment of the present invention, the second unit further comprises a spiral flow controller to promote the reaction in the hydrothermal humification device.

[0127] According to the implementation scheme of the utility model, the hydrothermal humification device is preferably a horizontal tube reaction device.

[0128] According to an embodiment of the utility model, 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.

[0129] According to the embodiment of the utility model, 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.

[0130] According to the embodiment of the utility model, 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.

[0131] According to the embodiment of the utility model, 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 mixture 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, so as to cool and / or purify the hydrothermal humification gas phase material.

[0132] According to the implementation scheme of the utility model, the outlet of the hydrothermal humification solid-liquid-gas mixture material of the hydrothermal humification device is connected to the inlet of the hydrothermal humification product separation device.

[0133] According to the embodiment of the utility model, 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.

[0134] According to the embodiment of the utility model, 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.

[0135] According to the implementation scheme of the utility model, 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.

[0136] According to the embodiment of the utility model, the hydrothermal humification solid-liquid-gas mixture material comprises a mixture of solid material, liquid material and gas material.

[0137] According to an embodiment of the utility model, 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.

[0138] According to an embodiment of the utility model, 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 such as humin slurry.

[0139] According to the embodiment of the utility model, the solid-liquid separation device is provided with at least one hydrothermal humification liquid phase material outlet to provide hydrothermal humification liquid phase products such as humic acid liquid.

[0140] According to an embodiment of the utility model, 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.

[0141] As an example, 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.

[0142] According to the implementation scheme of the utility model, 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.

[0143] According to an embodiment of the utility model, the second unit 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.

[0144] According to an embodiment of the utility model, the second unit further includes one or more conveying devices to convey one, two or three of the gas phase material, solid phase material and gas phase material mentioned above to the corresponding device of the second unit for processing. Preferably, such a conveying device can be arranged between every two devices. It should be understood by those skilled in the art that such a conveying device is known in the art, and for this reason, the utility model does not particularly limit the specific structure of the conveying device, as long as it can effectively convey the material to the desired device.

[0145] According to the embodiment of the utility model, when the material needs to be cooled, circulating water can be selected for cooling. For this reason, the cooling device of the utility model can also be provided with a pipeline for circulating cooling water.

[0146] According to the embodiment of the utility model, 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, such as 60-120 min.

[0147] According to an embodiment of the present invention, the product of the second unit comprises humic acid liquid and humin slurry.

[0148] According to an embodiment of the present invention, the product of the second unit can be subjected to filter pressing, drying and / or granulation devices to efficiently convert the biomass into an artificial humic acid biopolymer material similar to humus.

[0149] According to an embodiment of the present utility model, the second unit may further include a storage device for storing the obtained humin slurry, humic acid composite zeolite-based synthetic material and humic acid liquid product.

[0150] 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 biomass degradation through biological, physical and chemical processes in nature. The humic acid complex combined with soil minerals can stabilize the organic carbon in the soil for thousands of years. Lignin is converted into a humus-like polymer under copolymerization through the HTH process in the second unit. The product of this biopolymer can also modify the product molecular composition and molecular weight by adding solid acid catalytic materials, that is, in the process of synthesizing humic acid by HTH or HTC, the product molecular composition and molecular weight can be modified by adding solid acid catalytic materials, so that the synthetic material has higher biological redox interaction activity. Meet the requirements for the active quality of humic acid products.

[0151]

Unit 3

[0152] The third unit is the C-HTH (C-HydroThermal Humification, C-HTH) catalytic hydrothermal humification process unit, which is used to synthesize modified water coke (artificial humin); under the action of two types of catalytic materials, solid acid catalyst and biodepolymerization slurry, humin slurry can synthesize modified water coke with performance similar to that of natural humin.

[0153] The third unit is located downstream of the discharge port of the second unit, and is connected to the discharge port of the sixth unit and the discharge port of the fifth unit upstream.

[0154] The third unit is a catalytic hydrothermal humification unit designed for a variety of reaction materials. This unit can modify and adjust the humin slurry from the second unit with a solid acid catalyst to treat biomass reaction materials with high and low salt contents respectively. Humin is modified by the added solid acid catalyst during the C-HTH process and converted into a carbon compound with a sponge-like structure, namely modified water coke. The performance of the modified water coke 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 water coke and humic acid can more stably or effectively assist in the degradation or inactivation of toxic substances in the soil; the modified water coke prepared by this unit combined with humic acid can buffer the soil pH, release carbon dioxide, and play a role in buffering the concentration of hydrogen ions in the soil. The composition of modified water coke, 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 fertilizer, promoting plant growth, plant irrigation, etc., and can achieve good results.

[0155] According to an embodiment of the utility model, the third unit is used for catalytic hydrothermal humification (C-HTH) reaction to produce artificial humin.

[0156] According to an embodiment of the present invention, the third unit includes a catalytic hydrothermal humification device, or includes a depolymerization device and a catalytic hydrothermal humification device disposed downstream of the depolymerization device.

[0157] According to the implementation scheme of the utility model, the catalytic hydrothermal humification device is arranged 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 be directly processed by the catalytic hydrothermal humification device.

[0158] Those skilled in the art should understand that the catalytic hydrothermal humification device disposed downstream of the depolymerization device as described herein may include not only a method of directly subjecting the material output from the depolymerization device to treatment by the catalytic hydrothermal humification device, but may also include a method of directly entering the material into the catalytic hydrothermal humification device for treatment, or subjecting the material output from the depolymerization device to treatment by first other devices and then by the catalytic hydrothermal humification device. The above-mentioned different methods should all be understood as optional methods covered by "the catalytic hydrothermal humification device disposed downstream of the depolymerization device". Therefore, according to the embodiment of the utility model, the depolymerization device may be directly connected or not directly connected to the catalytic hydrothermal humification device.

[0159] According to the embodiment of the utility model, a buffer separation device and / or other devices may be provided between the depolymerization device and the downstream catalytic hydrothermal humification device. For example, when the depolymerization device is not directly connected to the catalytic hydrothermal humification device, the material output from the depolymerization device may be first processed by the buffer separation device or other devices, and then processed by the catalytic hydrothermal humification device.

[0160] According to an embodiment of the present invention, the buffer separation device may be a gas-liquid buffer separator, such as a gas-liquid buffer separator known to those skilled in the art.

[0161] According to an embodiment of the utility model, the third unit 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 (such as 1. humin slurry; 2. solid acid catalytic material; 3. wet biomass homogenate without municipal sludge).

[0162] According to an embodiment of the present invention, the solid-liquid mixture material contains organic carbon.

[0163] According to the embodiment of the utility model, the third unit can be used to process various materials containing organic carbon, such as humin slurry, agricultural residues (biomass solid waste), wet biomass, etc. For example, the material containing organic carbon can be selected from humin slurry, wet biomass homogenate without municipal sludge, restaurant kitchen waste, kitchen waste, animal digestive fluid feces, water body sediment, wood waste residue, crop straw, peat, lignite, bituminous coal, etc., containing one or a mixture of two or more of the above organic carbon materials.

[0164] For example, when the material containing organic carbon is selected from food waste, kitchen waste, animal digestive fluid and feces, water body sediment, wood waste residue, crop straw, etc., it can be first depolymerized and then catalytically carbonized. Alternatively, when the material containing organic carbon is selected from humin slurry, wet biomass homogenate without municipal sludge, peat, lignite, bituminous coal, etc., it can be directly catalytically carbonized.

[0165] According to the embodiment of the utility model, the depolymerization device may be provided with at least one feed port, so that the material provided by the feed device enters the depolymerization device.

[0166] According to an embodiment of the utility model, the material in the feeding device can directly enter the depolymerization device. Alternatively, as another option, a raw material mixer, a preheating mixer and / or a mixing liquid storage tank are arranged 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 liquid storage tank before entering the depolymerization device.

[0167] According to an embodiment of the present invention, the third unit may further include a steam generating device to provide the depolymerization device with steam required for the depolymerization reaction.

[0168] According to the embodiment of the utility model, the steam generating device can also provide the steam required for the reaction of the catalytic hydrothermal humification device.

[0169] According to an embodiment of the utility model, the depolymerization device may be provided with at least one air inlet so that the steam in the steam generating device can enter the depolymerization device.

[0170] According to an embodiment of the utility model, the depolymerization device may also be provided with at least one additive feed port, so that the additives required for the depolymerization reaction can enter the depolymerization device.

[0171] Alternatively, as another option, the additive may also enter the depolymerization device through the feed port of the solid-liquid mixture, as long as it can participate in the depolymerization reaction.

[0172] According to the embodiment of the utility model, the depolymerization device may also be provided with at least one outlet for depolymerization gas phase material and at least one outlet for depolymerization non-gas phase material.

[0173] Preferably, the depolymerized gaseous material comprises tail gas generated by the depolymerization reaction, and the depolymerized non-gaseous material comprises a mixture of solid-phase material and liquid-phase material which needs to be further processed in a buffer separation device and / or a catalytic carbonization device after being processed by a depolymerization device.

[0174] According to an embodiment of the utility model, 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 phase gas cooling device and / or a first gas phase purification device, preferably including a first phase cooling device and a first gas phase purification device.

[0175] According to the embodiment of the utility model, the condensate obtained by cooling the depolymerized 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.

[0176] According to the embodiment of the utility model, the depolymerization gas phase treatment device can be connected to the discharge device, so that the gas obtained after being treated by the depolymerization gas phase treatment device enters the discharge device for discharge.

[0177] According to an embodiment of the utility model, the third unit further comprises a spiral flow controller to promote the reaction in the depolymerization device and / or the catalytic hydrothermal humification device.

[0178] According to the embodiment of the utility model, the depolymerization device and / or the catalytic hydrothermal humification device is preferably a horizontal tube reaction device.

[0179] According to an embodiment of the utility model, the catalytic hydrothermal humification device is provided with at least one air inlet, so that the steam in the steam generating device enters the catalytic hydrothermal humification device.

[0180] According to the implementation scheme of the utility model, a hydrothermal humification product separation device is further provided downstream of the catalytic hydrothermal humification device to separate the gas phase material from the non-gas phase material in the material produced by the catalytic hydrothermal humification device.

[0181] According to the embodiment of the utility model, 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.

[0182] According to the embodiment of the utility model, 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 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.

[0183] According to the implementation scheme of the utility model, the solid-liquid-gas mixture material outlet of the catalytic hydrothermal humification device is connected to the inlet of the separation device.

[0184] According to the embodiment of the utility model, 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 mixture 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 to cool and / or purify the hydrothermal humification gas phase material.

[0185] According to the embodiment of the utility model, 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 delivery pipeline.

[0186] According to the implementation scheme of the utility model, 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.

[0187] According to an embodiment of the present utility model, the solid-liquid-gas mixture material comprises a mixture of solid material, liquid material and gas material.

[0188] According to an embodiment of the utility model, 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.

[0189] According to an embodiment of the present utility model, the solid-liquid separation device is provided with at least one solid phase material outlet to provide a solid phase product.

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

[0191] According to an embodiment of the utility model, 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 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.

[0192] As an example, 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.

[0193] According to the implementation scheme of the utility model, 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.

[0194] According to an embodiment of the utility model, the hydrothermal system 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 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.

[0195] According to an embodiment of the utility model, the hydrothermal system further comprises one or more conveying devices to convey one, two or three of the gas phase material, solid phase material and gas phase material described above to the corresponding device in the system for processing. Preferably, such a conveying device can be arranged between every two devices. It should be understood by those skilled in the art that such a conveying device is known in the art, and for this reason, the utility model does not particularly limit the specific structure of the conveying device, as long as it can effectively convey the material to the desired device.

[0196] According to the embodiment of the utility model, when the material needs to be cooled, circulating water can be selected for cooling. For this reason, the cooling device of the utility model can also be provided with a pipeline for circulating cooling water.

[0197] According to the embodiment of the present invention, the temperature for depolymerization of 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.

[0198] According to the embodiment of the utility model, 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, such as 60-120 min.

[0199] According to an embodiment of the utility model, the third unit may also include one, two or more pre-treatment devices for pre-treating the organic carbon-containing material before depolymerization (or referred to as "pre-treatment"). For example, the pre-treatment includes but is not limited to pre-treating the organic carbon-containing material by crushing, pulping, depolymerization, extraction, soaking, etc.

[0200] According to an embodiment of the utility model, the additive may be an additional additive required for any of the devices in the third unit to react or process, 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 a zeolite-based solid-phase acid catalyst, such as a zeolite-based solid-phase acid-catalyzed powdered catalyst or an oxygen carrier.

[0201] According to an embodiment of the present utility model, the solid acid catalyst may be the fly ash zeolite-based composite nano oxygen carrier described in Chinese patent application No. 202311217726.6.

[0202] According to the implementation scheme of the utility model, the fly ash is the tiny ash particles discharged during the combustion of fuel, which may or may not contain unburned carbonaceous particles, and the unburned carbonaceous particles are also called fly ash or smoke ash. In a preferred embodiment, the fly ash is taken from the combustion fly ash produced by the 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 the fly ash landfill and the ultra-fine powder raw material prepared from the boiler combustion residue; preferably, the fly ash generated immediately by the pulverized coal boiler of the power plant is selected. For example, it is the fly ash collected by the dust collector at the rear end of the coal-fired boiler.

[0203] According to an embodiment of the utility model, the oxygen carrier is prepared from fly ash. Preferably, the oxygen carrier is a dual-phase catalytic functional oxygen carrier used in a novel chemical looping combustion.

[0204] According to an embodiment of the utility model, the solid acid catalyst or oxygen carrier comprises a metal oxide and a carrier, for example, wherein 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, the metal oxide is uniformly distributed (or dispersed) in the crystal structure of the carrier.

[0205] It should be understood by those skilled in the art that when a dispersant is used, the dispersant may be selected from dispersants known to those skilled in the art, as long as it helps to disperse the metal oxide in the support.

[0206] According to an embodiment of the present invention, the solid acid catalyst or oxygen carrier is referred to as a primary dispersion in the embodiment of the present invention because it has the above-mentioned dispersed structure.

[0207] According to an embodiment of the present invention, the oxygen carrier has a crystal structure of FAU zeolite.

[0208] According to an embodiment of the present utility model, the metal oxide includes but is not limited to an oxide 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, aluminum oxide; as an example, the metal oxide is ferric oxide, zinc oxide, aluminum oxide.

[0209] According to the embodiment of the utility model, when the metal oxide is ferric oxide, it may have a nanocrystalline particle structure of γ-Fe2O3, α-Fe2O3, or γ-Fe3O4.

[0210] According to an embodiment of the utility model, the metal of the metal oxide is derived from the metal contained in the fly ash itself, or an added metal or metal oxide. For example, the metal contained in the fly ash itself is derived from the metal in the material containing organic carbon.

[0211] According to an embodiment of the present invention, the metal oxide may be a nanoparticle. For example, the size of the nanoparticle is 0.1-100 nm, such as 1-50 nm, and exemplified by 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50 nm.

[0212] According to an embodiment of the present invention, the metal oxide nanoparticles are ferric oxide nanoparticles with a particle size of 3-5 nm.

[0213] According to the embodiment of the present invention, the particle shape of the metal oxide can be circular, ellipsoidal or other regular or irregular shapes.

[0214] According to the embodiment of the utility model, the oxygen carrier is a micro-nano material, that is, has a micro-nano crystal structure.

[0215] According to an embodiment of the present invention, the mass ratio of the metal oxide to the oxygen carrier is 5 to 35 wt%, for example, 10 wt%, 15 wt%, 20 wt%, 25 wt%, or 30 wt%.

[0216] According to an embodiment of the present utility model, the particle size of the oxygen carrier is 0.075 mm to 0.2 mm, for example, 100 μm, 120 μm, 150 μm, 180 μm.

[0217] According to the implementation scheme of the utility model, the oxygen carrier is prepared from fly ash as raw material through a fusion polymerization (melt polymerization)-hydrothermal double-stage alkali conversion method.

[0218] According to an embodiment of the utility model, the oxygen carrier also includes one or more metal complexes or non-metallic 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 with or compensate for the functions of these metal elements.

[0219] According to the embodiment of the utility model, the metal element of the metal complex can be selected from rare earth metal elements and / or semi-metal elements; for example, the rare earth metal element is lanthanum (La) or cerium (Ce), preferably cerium; for example, the semi-metal element is silicon (Si).

[0220] According to the implementation scheme of the present utility model, the metal complex 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, and titanium, preferably compounds of aluminum and zinc, and more preferably aluminum oxide and zinc oxide.

[0221] In one embodiment, the rare earth metal element is derived from its salt or oxide, and the semi-metal element is derived from its oxide (eg, silicon dioxide).

[0222] In one embodiment, the metal compound is the corresponding metal salt or oxide.

[0223] According to an embodiment of the present invention, the metal complex is a nano-scale metal oxide, such as nano-cerium oxide, nano-aluminum oxide and / or nano-zinc oxide.

[0224] According to an embodiment of the utility model, the oxygen carrier may further include an additive. For example, the additive is one or more of an inorganic acid, an inorganic base, etc. For example, 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.

[0225] According to an embodiment of the present utility model, the solid acid catalyst may be a nanocomposite zeolite material described in Chinese patent application 202310381676.9.

[0226] According to the embodiment of the utility model, the nano-scale crystal structure of the nano-composite zeolite material is a FAU / Zeolite structure, preferably a FAU / Zeolite Y structure.

[0227] According to an embodiment of the present invention, the nanocomposite zeolite material has micro-mesoporous cage void space.

[0228] According to an embodiment of the present utility model, the nanocomposite zeolite material is aluminosilicate hydrate.

[0229] According to an embodiment of the present invention, the nanocomposite zeolite material further comprises one, two or more of the following elements: magnesium (Mg), iron (Fe), zinc (Zn), molybdenum (Mo), boron (B), selenium (Se), etc. Preferably, the elements are added to the nanocomposite zeolite material in the form of their chlorides (e.g., zinc chloride, iron chloride) as raw materials.

[0230] According to an embodiment of the present invention, the nanocomposite zeolite material is a Fugarst zeolite type structure (FAU).

[0231] According to the implementation scheme of the utility model, the nano-composite zeolite material has a three-level pore structure: the pore diameter of the first-level pore structure does not exceed 10nm, for example, does not exceed 5nm, and is preferably less than 2nm (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 50nm; the pore diameter of the third-level pore structure (also called macropores) is greater than 50nm, for example, greater than 50nm and not more than 500nm, such as 200nm.

[0232] According to the embodiment of the utility model, the sum of the specific surface areas of the nanocomposite zeolite material is 150 to 1500 m 2 / g, for example 300~1200m 2 / g, such as 500~1000m 2 / g.

[0233] According to an embodiment of the present utility model, the cation exchange capacity (CEC) of the nanocomposite zeolite material is 150-250 cmol (+) / kg.

[0234] According to an embodiment of the present invention, the pore volume of the nanocomposite zeolite material accounts for more than 50%, such as more than 60%, such as 65-80%.

[0235] According to an embodiment of the present invention, the mass density of the nanocomposite zeolite material is 2.1-2.2 g / cc.

[0236] According to an embodiment of the present utility model, the nanocomposite zeolite material has water holding performance (water holding performance 50 wt %).

[0237] According to an embodiment of the utility model, the nanocomposite zeolite material is insoluble in water at any pH. Alternatively, the nanocomposite zeolite material has the characteristics of acid and alkali resistance, that is, it is neither soluble in alkali (high pH) nor in acid (low pH).

[0238] According to the implementation scheme of the utility model, 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 generated immediately by pulverized coal boilers in power plants is selected.

[0239] According to the embodiment of the utility model, each device in the third unit can be optionally independently provided with a feed port for feeding additives. 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 is mixed with the additive in the depolymerization reaction device and then reacts.

[0240] According to an embodiment of the present invention, the additive is a dispersion in which a zeolite-based carrier is used as a carrier and a metal oxide is primarily dispersed in the zeolite-based carrier.

[0241] According to an embodiment of the utility model, 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 zeolite-based primary dispersion of the additive is further dispersed in water coke for a secondary time.

[0242] According to the implementation scheme of the utility model, 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.

[0243] According to the implementation scheme of the utility model, 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 to 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 to 120 min, for example, 20 to 60 min.

[0244] According to an embodiment of the present utility model, the product of the third unit comprises humin slurry, humic acid composite zeolite-based synthetic material and humic acid liquid.

[0245] According to the embodiment of the utility model, the product of the third unit can be passed through a filter press, drying and / or granulation device to prepare a composition containing modified water char, humic acid and / or organic carbon medium nutrients that can be widely used for soil fertilizer, promoting the ecological balance of soil microorganisms and soil animals, promoting the degradation or inactivation of toxic substances in the soil, improving soil pH, plant fertilizer, promoting plant growth, plant irrigation, etc., and can achieve good results.

[0246] According to an embodiment of the present utility model, the third unit may further include a storage device for storing the obtained humin slurry, humic acid composite zeolite-based synthetic material and humic acid liquid product.

[0247] Unit 5○ Solid acid catalysis can be added in any chemical direction for modification and adjustment, and can also be used to treat high-salt and low-salt reaction materials at the same time. Biomass raw materials have a significant effect of accelerating humification under the action of solid acid catalytic materials. Under solid acid catalytic conditions, humin can be converted into a carbon compound with a sponge-like structure, namely modified water coke, which has similar performance to natural humin and can provide the required energy and mineral requirements for soil microorganisms and soil animals. The mixture of modified water coke and soil humus can more stably or effectively assist the degradation or inactivation of toxic substances in the soil; the composition of modified water coke combined with humus substances and / or organic carbon medium nutrients prepared by the third unit can buffer soil pH, release carbon dioxide, and play a role in buffering soil hydrogen ion concentration; and 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.

[0248]

Unit 4

[0249] The fourth unit is the C-HTC catalytic hydrothermal carbonization unit, which is used for the production of oxygen-carrying carbon-based catalytic combustion-supporting materials. The raw materials containing heavy metals are carbonized separately for boiler combustion only.

[0250] The fourth unit is located at the most downstream of the process flow, connecting the discharge ports of the third unit, the seventh unit, and the fifth unit; it is the output end of the oxygen-carrying carbon-based catalytic combustion-supporting materials.

[0251] Solid acid catalysts can promote the HTC carbonization reaction of biomass and increase the efficiency by 30%; co-liquid carbonization Co-HTC can improve the combustion quality and cleanliness of the product. The modification of water coke by catalytic carbonization can produce carbon-based raw materials with good gasification effect. The dual-phase catalytic function of metal oxides supported by zeolite can catalyze the C-HTC process of this fourth unit to improve the carbonization rate and efficiently produce oxygen-carrying carbon-based catalytic combustion-supporting materials.

[0252] According to the implementation scheme of the utility model, the fourth unit is used for catalytic hydrothermal carbonization (Catalytic Hydro Thermal Carbonization, referred to as C-HTC).

[0253] According to an embodiment of the present invention, the fourth unit includes a catalytic carbonization device, or includes a depolymerization device and a catalytic carbonization device disposed downstream of the depolymerization device.

[0254] According to the embodiment of the utility model, 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 be directly processed by the catalytic carbonization device.

[0255] Those skilled in the art should understand that the catalytic carbonization device disposed downstream of the depolymerization device as described herein may include not only a method of directly subjecting the material output from the depolymerization device to treatment by the catalytic carbonization device, but also a method of directly entering the material into the catalytic carbonization device for treatment, or subjecting the material output from the depolymerization device to treatment by other devices first, and then by the catalytic carbonization device. The above-mentioned different methods should all be understood as optional methods covered by "the catalytic carbonization device is disposed downstream of the depolymerization device". Therefore, according to the embodiment of the utility model, the depolymerization device and the catalytic carbonization device may be directly connected or not directly connected.

[0256] According to the embodiment of the utility model, a buffer separation device and / or other devices may be provided between the depolymerization device and the downstream catalytic carbonization device. For example, when the depolymerization device is not directly connected to the catalytic carbonization device, the material output from the depolymerization device may be first processed by the buffer separation device or other devices, and then processed by the catalytic carbonization device.

[0257] According to an embodiment of the present invention, the buffer separation device may be a gas-liquid buffer separator, such as a gas-liquid buffer separator known to those skilled in the art.

[0258] According to an embodiment of the utility model, 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 mixture (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).

[0259] According to an embodiment of the present invention, the solid-liquid mixture material contains organic carbon.

[0260] According to the implementation scheme of the utility model, the fourth unit can be used to process materials containing organic carbon, such as humin slurry, or slurry prepared from urban garbage (organic solid waste), wet biomass, etc. For example, the material containing organic carbon can be selected from humin slurry, or slurry prepared from one, two or more materials containing organic carbon such as municipal sludge leachate, urban garbage, domestic garbage, restaurant kitchen waste, kitchen waste, municipal feces, sewage treatment sludge, water body sediment, garbage leachate, wood waste residue, crop straw, peat, lignite, bituminous coal, etc., or a mixture of slurries.

[0261] For example, when the material containing organic carbon is selected from domestic waste, restaurant waste, kitchen waste, municipal feces, sewage treatment sludge, water body sediment, garbage leachate, wood waste residue, crop straw and other raw materials, it can be pulped first, then depolymerized, and then catalytically carbonized. Alternatively, when the material containing organic carbon is selected from slurries after pulping such as humin slurry, peat, lignite, bituminous coal, etc., it can be directly catalytically carbonized.

[0262] According to the embodiment of the utility model, the depolymerization device may be provided with at least one slurry feed port, so that the slurry material provided by the feed device can enter the depolymerization device.

[0263] According to the embodiment of the utility model, the material in the feeding device can directly enter the depolymerization device. Alternatively, as another option, a raw material mixer, a preheating mixer and / or a mixing liquid storage tank are arranged between the feeding device and the depolymerization device, so that the material in the feeding device passes through the raw material slurry, the mixer, the preheating mixer and / or the mixing liquid storage tank before entering the depolymerization device.

[0264] According to an embodiment of the utility model, the hydrothermal carbonization system may further include a steam generating device to provide the depolymerization device with steam required for the depolymerization reaction.

[0265] According to the embodiment of the utility model, the steam generating device can also provide the steam required for the carbonization reaction to the catalytic carbonization device.

[0266] According to an embodiment of the utility model, the depolymerization device may be provided with at least one air inlet so that the steam in the steam generating device can enter the depolymerization device.

[0267] According to an embodiment of the utility model, the depolymerization device may also be provided with at least one additive feed port, so that the additives required for the depolymerization reaction can enter the depolymerization device.

[0268] Alternatively, as another option, the additive may also enter the depolymerization device through the feed port of the solid-liquid mixture, as long as it can participate in the depolymerization reaction.

[0269] According to the embodiment of the utility model, the depolymerization device may also be provided with at least one outlet for depolymerization gas phase material and at least one outlet for depolymerization non-gas phase material.

[0270] Preferably, the depolymerized gaseous material comprises tail gas generated by the depolymerization reaction, and the depolymerized non-gaseous material comprises a mixture of solid-phase material and liquid-phase material which needs to be further processed in a buffer separation device and / or a catalytic carbonization device after being processed by a depolymerization device.

[0271] According to an embodiment of the utility model, 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 phase gas cooling device and / or a first gas phase purification device, preferably including a first phase cooling device and a first gas phase purification device.

[0272] According to the embodiment of the utility model, the condensate obtained by cooling the depolymerized 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.

[0273] According to the embodiment of the utility model, the depolymerization gas phase treatment device can be connected to the discharge device, so that the gas obtained after being treated by the depolymerization gas phase treatment device enters the discharge device for discharge.

[0274] According to an embodiment of the present invention, the fourth unit further comprises a spiral flow controller to promote the reaction in the depolymerization device and / or the catalytic carbonization device.

[0275] According to an embodiment of the present utility model, the depolymerization device and / or the catalytic carbonization device is preferably a horizontal tube reaction device.

[0276] According to an embodiment of the utility model, the catalytic carbonization device is provided with at least one air inlet so that the steam in the steam generating device can enter the catalytic carbonization device.

[0277] According to an embodiment of the utility model, a carbonization product separation device is further provided downstream of the catalytic carbonization device to separate gaseous materials from non-gaseous materials in the materials produced by the catalytic carbonization device.

[0278] According to an embodiment of the utility model, a carbonized gas phase treatment device is further provided downstream of the carbonized product separation device. The carbonized 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.

[0279] According to the embodiment of the utility model, 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 mixture 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.

[0280] According to the implementation scheme of the utility model, the outlet of the carbonized solid-liquid-gas mixture material of the catalytic carbonization device is connected to the inlet of the carbonization product separation device.

[0281] According to the embodiment of the utility model, the carbonized product separation device is provided with at least one carbonized gas phase material outlet and at least one carbonized solid-liquid-gas mixture 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.

[0282] According to the embodiment of the utility model, 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 the raw material mixer. Therefore, the carbonized gas phase processing device can be connected to the raw material mixer through a liquid phase delivery pipeline.

[0283] According to the embodiment of the utility model, the carbonization 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 carbonization gas phase treatment device enters the discharge device for discharge.

[0284] According to an embodiment of the present utility model, the carbonized solid-liquid-gas mixture material comprises a mixture of solid material, liquid material and gas material.

[0285] According to an embodiment of the utility model, 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 mixture is connected to the inlet of the solid-liquid separation device, so that the carbonized solid phase material and the carbonized liquid phase material in the carbonized solid-liquid-gas mixture are separated.

[0286] According to the implementation scheme of the utility model, the solid-liquid separation device is provided with at least one outlet for carbonized solid phase material (such as solid oxygen-carrying carbon-based catalytic combustion-supporting material and part of the output cycle) to provide a carbonized solid phase product.

[0287] According to the embodiment of the utility model, the solid-liquid separation device is provided with at least one carbonized liquid phase material outlet to provide a carbonized liquid phase product.

[0288] According to an embodiment of the utility model, 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 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.

[0289] As an example, 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.

[0290] According to an embodiment of the present utility model, 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.

[0291] According to an embodiment of the utility model, 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. 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.

[0292] According to an embodiment of the present invention, the hydrothermal carbonization system further comprises one or more conveying devices to convey one, two or three of the gas phase material, solid phase material and gas phase material mentioned above to the corresponding device in the hydrothermal carbonization system for processing. Preferably, such a conveying device can be provided between every two devices. It should be understood by those skilled in the art that such a conveying device is known in the art, and for this reason, 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.

[0293] According to the embodiment of the utility model, when the material needs to be cooled, circulating water can be selected for cooling. For this reason, the cooling device of the utility model can also be provided with a pipeline for circulating cooling water.

[0294] According to the embodiment of the present invention, the temperature for depolymerization of 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.

[0295] According to the embodiment of the present utility model, 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, such as 60-120 min.

[0296] According to an embodiment of the utility model, the fourth unit may also include one, two or more pre-treatment devices for pre-treating the organic carbon-containing material before depolymerization (or referred to as "pre-treatment"). For example, the pre-treatment includes but is not limited to pre-treating the organic carbon-containing material by crushing, pulping, depolymerization, extraction, soaking, etc.

[0297] According to an embodiment of the utility model, the additive may be an additional additive required for any of the devices in the fourth unit to react or process, 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 a zeolite-based solid phase acid catalyst, such as a zeolite-based solid phase acid catalytic powdered catalyst or an oxygen carrier.

[0298] According to an embodiment of the present utility model, the solid acid catalyst may be the fly ash zeolite-based composite nano oxygen carrier described in Chinese patent application No. 202311217726.6.

[0299] According to the implementation scheme of the utility model, the fly ash is the tiny ash particles discharged during the combustion of fuel, which may or may not contain unburned carbonaceous particles, and the unburned carbonaceous particles are also called fly ash or smoke ash. In a preferred embodiment, the fly ash is taken from the combustion fly ash produced by the 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 the fly ash landfill and the ultra-fine powder raw material prepared from the boiler combustion residue; preferably, the fly ash generated immediately by the pulverized coal boiler of the power plant is selected. For example, it is the fly ash collected by the dust collector at the rear end of the coal-fired boiler.

[0300] According to an embodiment of the utility model, the oxygen carrier is prepared from fly ash. Preferably, the oxygen carrier is an oxygen carrier with a dual-phase catalytic function used in a novel chemical looping combustion.

[0301] According to an embodiment of the utility model, the solid acid catalyst or oxygen carrier comprises a metal oxide and a carrier, for example, wherein 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, the metal oxide is uniformly distributed (or dispersed) in the crystal structure of the carrier.

[0302] It should be understood by those skilled in the art that when a dispersant is used, the dispersant may be selected from dispersants known to those skilled in the art, as long as it helps to disperse the metal oxide in the support.

[0303] According to an embodiment of the present invention, the solid acid catalyst or oxygen carrier is referred to as a primary dispersion in the embodiment of the present invention because it has the above-mentioned dispersed structure.

[0304] According to an embodiment of the present invention, the oxygen carrier has a crystal structure of FAU zeolite.

[0305] According to an embodiment of the present utility model, the metal oxide includes but is not limited to an oxide 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, aluminum oxide; as an example, the metal oxide is ferric oxide, zinc oxide, aluminum oxide.

[0306] According to the embodiment of the utility model, when the metal oxide is ferric oxide, it may have a nanocrystalline particle structure of γ-Fe2O3, α-Fe2O3, or γ-Fe3O4.

[0307] According to an embodiment of the utility model, the metal of the metal oxide is derived from the metal contained in the fly ash itself, or an added metal or metal oxide. For example, the metal contained in the fly ash itself is derived from the metal in the material containing organic carbon.

[0308] According to an embodiment of the present invention, the metal oxide may be a nanoparticle. For example, the size of the nanoparticle is 0.1-100 nm, such as 1-50 nm, and exemplified by 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50 nm.

[0309] According to an embodiment of the present invention, the metal oxide nanoparticles are ferric oxide nanoparticles with a particle size of 3-5 nm.

[0310] According to the embodiment of the present invention, the particle shape of the metal oxide can be circular, ellipsoidal or other regular or irregular shapes.

[0311] According to the embodiment of the utility model, the oxygen carrier is a micro-nano material, that is, has a micro-nano crystal structure.

[0312] According to an embodiment of the present invention, the mass ratio of the metal oxide to the oxygen carrier is 5 to 35 wt%, for example, 10 wt%, 15 wt%, 20 wt%, 25 wt%, or 30 wt%.

[0313] According to an embodiment of the present utility model, the particle size of the oxygen carrier is 0.075 mm to 0.2 mm, for example, 100 μm, 120 μm, 150 μm, 180 μm.

[0314] According to the implementation scheme of the utility model, the oxygen carrier is prepared from fly ash as raw material through a fusion polymerization (melt polymerization)-hydrothermal double-stage alkali conversion method.

[0315] According to an embodiment of the utility model, the oxygen carrier also includes one or more metal complexes or non-metallic 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 with or compensate for the functions of these metal elements.

[0316] According to the embodiment of the utility model, the metal element of the metal complex can be selected from rare earth metal elements and / or semi-metal elements; for example, the rare earth metal element is lanthanum (La) or cerium (Ce), preferably cerium; for example, the semi-metal element is silicon (Si).

[0317] According to the implementation scheme of the present utility model, the metal complex 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, and titanium, preferably compounds of aluminum and zinc, and more preferably aluminum oxide and zinc oxide.

[0318] In one embodiment, the rare earth metal element is derived from its salt or oxide, and the semi-metal element is derived from its oxide (eg, silicon dioxide).

[0319] In one embodiment, the metal compound is the corresponding metal salt or oxide.

[0320] According to an embodiment of the present invention, the metal complex is a nano-scale metal oxide, such as nano-cerium oxide, nano-aluminum oxide and / or nano-zinc oxide.

[0321] According to an embodiment of the utility model, the oxygen carrier may further include an additive. For example, the additive is one or more of an inorganic acid, an inorganic base, etc. For example, 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.

[0322] According to an embodiment of the present utility model, the solid acid catalyst may be a nanocomposite zeolite material described in Chinese patent application 202310381676.9.

[0323] According to the embodiment of the utility model, the nano-scale crystal structure of the nano-composite zeolite material is a FAU / Zeolite structure, preferably a FAU / Zeolite Y structure.

[0324] According to an embodiment of the present invention, the nanocomposite zeolite material has micro-mesoporous cage void space.

[0325] According to an embodiment of the present utility model, the nanocomposite zeolite material is aluminosilicate hydrate.

[0326] According to an embodiment of the present invention, the nanocomposite zeolite material further comprises one, two or more of the following elements: magnesium (Mg), iron (Fe), zinc (Zn), molybdenum (Mo), boron (B), selenium (Se), etc. Preferably, the elements are added to the nanocomposite zeolite material in the form of their chlorides (e.g., zinc chloride, iron chloride) as raw materials.

[0327] According to an embodiment of the present invention, the nanocomposite zeolite material is a Fugarst zeolite type structure (FAU).

[0328] According to the implementation scheme of the utility model, the nano-composite zeolite material has a three-level pore structure: the pore diameter of the first-level pore structure does not exceed 10nm, for example, does not exceed 5nm, and is preferably less than 2nm (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 50nm; the pore diameter of the third-level pore structure (also called macropores) is greater than 50nm, for example, greater than 50nm and not more than 500nm, such as 200nm.

[0329] According to the embodiment of the utility model, the sum of the specific surface areas of the nanocomposite zeolite material is 150 to 1500 m 2 / g, for example 300~1200m 2 / g, such as 500~1000m 2 / g.

[0330] According to an embodiment of the present utility model, the cation exchange capacity (CEC) of the nanocomposite zeolite material is 150-250 cmol (+) / kg.

[0331] According to an embodiment of the present invention, the pore volume of the nanocomposite zeolite material accounts for more than 50%, such as more than 60%, such as 65-80%.

[0332] According to an embodiment of the present invention, the mass density of the nanocomposite zeolite material is 2.1-2.2 g / cc.

[0333] According to an embodiment of the present utility model, the nanocomposite zeolite material has water holding performance (water holding performance 50 wt %).

[0334] According to an embodiment of the utility model, the nanocomposite zeolite material is insoluble in water at any pH. Alternatively, the nanocomposite zeolite material has the characteristics of acid and alkali resistance, that is, it is neither soluble in alkali (high pH) nor in acid (low pH).

[0335] According to the implementation scheme of the utility model, 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 generated immediately by pulverized coal boilers in power plants is selected.

[0336] According to the embodiment of the utility model, each device in the fourth unit can be optionally independently provided with a feed port for feeding additives. 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 is mixed with the additive in the depolymerization reaction device and then reacts.

[0337] According to an embodiment of the present invention, the additive is a dispersion in which a zeolite-based carrier is used as a carrier and a metal oxide is primarily dispersed in the zeolite-based carrier.

[0338] According to an embodiment of the utility model, 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 zeolite-based primary dispersion of the additive is further dispersed in water coke for a secondary time.

[0339] According to the implementation scheme of the utility model, 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.

[0340] According to an embodiment of the utility model, 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 carbonization device can be reduced to 150 to 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 to 120 min, for example, 20 to 60 min.

[0341] According to an embodiment of the present utility model, the product of the fourth unit is the water coke slurry of the fourth unit containing the additive (such as a solid acid catalyst, preferably, the content of the solid acid catalyst is higher than 20%).

[0342] According to an embodiment of the utility model, the product can be filtered, dried and / or pelletized to prepare a water coke fuel product. Preferably, the particle size of the water coke fuel product can be adjusted to make it suitable for the requirements or standards of subsequent units.

[0343] According to an embodiment of the present invention, the fourth unit may further include a storage device for storing the obtained water coke fuel product.

[0344] The fourth unit in the utility model 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 fuel. The modified water coke catalytically carbonized is also a biomass energy fuel with high cleanliness and good gasification effect.

[0345] The utility model also provides a method for preparing a humic acid composite zeolite-based synthetic material, which is prepared by treating fly ash materials using the above-mentioned treatment system.

[0346] According to the implementation scheme of the utility model, the fly ash is the tiny ash particles discharged during the combustion of fuel, which may or may not contain unburned carbonaceous particles, and the unburned carbonaceous particles are also called fly ash or smoke ash. In a preferred embodiment, the fly ash is taken from the combustion fly ash produced by the 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 the fly ash landfill and the ultrafine powder raw material prepared from the boiler combustion residue; preferably, the fly ash generated immediately by the pulverized coal boiler of the power plant 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 selected from the clean treatment before the combustion of traditional boiler fuel (including low-value lignite, peat, biomass).

[0347] According to an embodiment of the present utility model, the humic acid composite zeolite-based synthetic material is the product of the third unit mentioned above.

[0348] According to an embodiment of the utility model, 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, for example, 1:1 to 5:1, and exemplified by 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, and 10:1.

[0349] According to the embodiment of the utility model, the preparation method of the humic acid composite zeolite-based synthetic material comprises the following steps:

[0350] (1) Using fly ash as raw material, preparing in the fifth unit an additive for preparing the first unit and / or the third unit and / or the fourth unit;

[0351] (2) Under the action of the additive prepared in the fifth unit, the lignin pulp is subjected to the first unit 3 of the CAFT humification heterogeneous catalytic Fenton reaction to separate the modified lignin similar to humic acid (such as Fenton catalytic modified lignin pulp);

[0352] (3) The modified lignin produced by the first unit is converted into artificial humic acid liquid and humin slurry in the second unit;

[0353] (4) Under the action of the additive prepared in the fifth unit, the humin slurry produced in the second unit and the wet biomass homogenate without municipal sludge are subjected to hydrothermal humification in the third unit to synthesize artificial humin, humic acid composite zeolite-based synthetic material and humic acid liquid;

[0354] (5) Under the action of the additive prepared in the fifth unit, the artificial humin slurry produced in the third unit and the wet biomass slurry containing municipal sludge are hydrothermally carbonized in the fourth unit to obtain a solid oxygen-carrying carbon-based catalytic combustion-supporting material.

[0355] According to the implementation scheme of the utility model, calculated based on the feed amount of fly ash material, the output of humic acid composite zeolite-based synthetic material in the product of the third unit is 3 to 10 times, preferably 6 times, of the feed amount of fly ash material.

[0356] The utility model also provides a fly ash processing method, which comprises utilizing the above processing system to process the fly ash material.

[0357] The utility model also provides application of the above processing system in preparing fertilizer (such as slow-release fertilizer).

[0358] The utility model also provides a slow-release fertilizer, comprising the humic acid composite zeolite-based synthetic material, wherein the nano composite zeolite material in the humic acid composite zeolite-based synthetic material serves as a carrier of the active components of the fertilizer.

[0359] The humic acid composite zeolite-based material prepared by the treatment system of the utility model can be used as a slow-release fertilizer and as a modifier for comprehensively enhancing soil fertility. At a cumulative application amount of no less than 2.5 metric tons per hectare over five years, the soil ammonia volatilization can be reduced by more than 50%, the soil moisture retention rate can be increased by 60%, and the soil available water storage capacity can be increased by 75%.

[0360] The utility model also provides a slow-release herbicide, which contains the humic acid composite zeolite-based material and the herbicide.

[0361] The utility model also provides the application of the above slow-release fertilizer or slow-release herbicide in the fields of soil and / or planting. For example, it can be used as soil fertilizer, promoting the ecological balance of soil microorganisms and soil animals, promoting the degradation or inactivation of toxic substances in the soil, improving soil pH, plant fertilizer, promoting plant growth, plant irrigation, etc. For example, the fertility of the slow-release fertilizer containing macronutrient cations according to the stoichiometric leaching amount is at least twice the fertility of the stoichiometric cation of the same macronutrient chemical.

[0362] According to an embodiment of the present invention, the slow-release fertilizer is used as soil fertilizer and / or plant fertilizer.

[0363] The utility model also provides a soil fertilizer, which contains the humic acid composite zeolite-based material, wherein the soil fertilizer can be a liquid-solid mixed fertilizer or a solid fertilizer.

[0364] The utility model also provides a method for preparing the soil fertilizer, which comprises preparing the soil fertilizer from raw materials containing the humic acid composite zeolite-based material.

[0365] The utility model also provides a soil conditioner, which contains the humic acid composite zeolite-based material, wherein the soil conditioner can be a liquid-solid mixed conditioner or a solid conditioner.

[0366] In one embodiment, the soil is sandy soil. When used to improve sandy soil, adding the soil conditioner containing the composite material can reduce the ammonia volatilization of sandy soil by 8%, and increase the water retention rate of sandy soil by 10% and the available water storage capacity by 15%.

[0367] In some embodiments, the soil conditioner is used to adjust soil physical properties, such as increasing soil water holding capacity and reducing soil water salinity.

[0368] In some embodiments, the soil conditioner is used to repair contaminated soil. In some soils contaminated by heavy metals or radioactive nuclei, composite materials doped with special elements can be used to repair radioactive contamination.

[0369] The utility model also provides a method for preparing the soil conditioner, which comprises preparing the soil conditioner from raw materials containing the humic acid composite zeolite-based material.

[0370] The utility model also provides a plant fertilizer, which contains the humic acid composite zeolite-based material, wherein the plant fertilizer can be a liquid-solid mixed fertilizer or a solid fertilizer.

[0371] The utility model also provides a method for preparing the plant fertilizer, which comprises preparing the plant fertilizer from a raw material containing the humic acid composite zeolite-based material.

[0372] The utility model also provides a plant growth agent containing the humic acid composite zeolite-based material.

[0373] The utility model also provides a method for preparing the plant growth agent, which comprises preparing the plant growth agent from a raw material containing the humic acid composite zeolite-based material.

[0374] The utility model also provides application of the humic acid composite zeolite-based material in wastewater treatment, for example, removing ammonia and / or heavy metal ions in wastewater.

[0375] The utility model also provides a wastewater treatment agent containing the humic acid composite zeolite-based material.

[0376] Beneficial effects:

[0377] (1) The utility model uses two types of waste produced by the front and rear ends of the coal-fired power boiler combustion system as the main raw materials, and cooperates with the synthesis process of artificial humic acid and artificial zeolite; integrating the process of loading beneficial mineral elements and macronutrients, the utility model can realize the large-scale production of humic acid composite zeolite-based ultra-high-efficiency salt-resistant and water-retaining ecological slow-release fertilizer. The humic acid high-efficiency slow-release ecological fertilizer of the utility model is a composite product composed 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 mass-produced in the form of solid particles (or powder) or liquid suspension commercial ecological fertilizer products. The ecological fertilizer of the utility model can be widely used in various cultivated soils (especially degraded cultivated lands with serious loss of organic carbon), and large-scale and long-term application will have a macroscopic effect of promoting the balance of soil microbial ecology and soil animal ecology; the processing system of the utility model uses large-scale coal-fired power enterprises with low-value coal, and takes the organic waste materials (low-value lignite, peat organic components) and fly ash inorganic waste materials produced by them as resource targets, and can realize the low-cost production of humic acid zeolite-based nutrient slow-release fertilizers on an industrial scale.

[0378] (2) The treatment system of the utility model can be applied to the technical transformation of traditional coal-fired boiler systems to improve the combustion quality, that is, to use the active organic matter in the separated coal fuel as the raw material for producing artificial humic acid, and to recycle organic waste that is harmful to combustion while achieving efficient and clean combustion of coal fuel.

[0379] (3) The treatment system of the utility model can be applied to the fly ash collection system of the traditional coal-fired boiler system; the collected fly ash solid waste can be recycled into high-value (dual-phase) solid acid catalytic materials, so as to realize the recycling of various metal elements in the fly ash, and at the same time improve the thermal-electric conversion efficiency of the unit, recover beneficial mineral elements and circulate back to feed the soil microecology.

[0380] (4) The treatment system of the utility model can also utilize wet biomass waste such as kitchen waste, kitchen waste, organic sludge, digestive fluid, etc. to realize the material and energy value of wet biomass organic carbon regeneration resources.

[0381] (5) The utility model coordinates the extraction process of separating the biopolymer components contained in low calorific value lignite with the pretreatment process of clean and quality-improving coal raw materials, that is, through the traditional power production link of clean treatment of coal raw materials, on the one hand, it achieves the effect of improving the combustion quality of power plant boilers and power production efficiency, and on the other hand, it provides scarce organic raw materials for the HTH process synthesis of artificial humic acid materials. The utility model not only realizes the pretreatment of clean and quality-improving coal raw materials for coal-fired power boiler systems, but also coordinates the separation of bulk biopolymer raw materials in low calorific value lignite, thereby providing favorable conditions for the industrial production of artificial humic acid materials.

[0382] (6) The utility model provides a thermal power plant that uses lignin-rich lignite, peat and other fuels, and uses organic waste produced by pretreatment of its fuel and inorganic waste such as fly ash (fly ash) produced by a dust removal device after combustion in its boiler as the main raw materials; and a process flow that is coordinated with the waste treatment process of the coal-fired power plant; the process flow of the utility model integrates the synthesis process of artificial humic acid and artificial zeolite, and couples the loading process of beneficial mineral elements and macronutrients, thereby realizing an efficient industrial process for producing humic acid composite zeolite-based ecological slow-release fertilizer products using coal-fired power plant waste as the main raw material.

[0383] (7) The fly ash produced by the boiler combustion process is the ash material after the mineral elements (ash content) contained in the above carbon-based fuels are burned at high temperature. Fly ash is similar to volcanic ash in form. The main SiO2 and Al2O3 elemental components contained in it can be regenerated by the advanced zeolite synthesis process and synthesized into high-value artificial zeolite materials for various purposes (molecular sieves, catalysts, adsorbents, etc.). The value of artificial zeolite lies first in its strong cation exchange capacity. As a highly active cation carrier medium; the cation exchange capacity of 7.5 tons of artificial zeolite is equivalent 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 for cation exchange capacity in the world's modern agricultural planting industry and the supply of cation exchange capacity in the fertilizer production industry. The difference between fly ash solid waste and synthetic zeolite made from silica and alumina ore is that the fly ash zeolite-based material synthesized by the former is heavy and enriched with a variety of beneficial mineral elements absorbed by plants in ancient times. Therefore, the fly ash solid waste from the coal power industry actually reserves industrial raw materials for the production of beneficial mineral nutrient fertilizer products for modern agriculture. The mature development of modern zeolite technology has made fly ash-synthesized zeolite materials a unique material containing a variety of alkali metals, transition metals and a variety of beneficial plant life mineral elements; because fly ash contains a variety of trace and trace oxides of beneficial mineral elements, fly ash-synthesized zeolites have far superior value in agricultural applications than natural zeolites and other raw material artificial zeolites. It can be foreseen that under the pressure of environmental non-point source pollution caused by salt loss of global commercial fertilizers and global land degradation, cheap fly ash zeolite materials as controlled release medium materials for agricultural fertilizers will be widely used as a commodity to replace fertilizer salts. The utility model realizes the online synthesis of fly ash zeolite materials through the fifth unit, and can realize the customization of the formula of doped metal oxides, that is, it can realize the catalytic performance in various thermochemical specific applications; that is, the beneficial metal elements in the fly ash are synthesized as components of zeolite-based materials, and the metal oxides supported by them can also be recycled as solid acid catalysts before finally returning to the land as mineral nutrients. The cyclic catalysis promotes the industrial system efficiency of the CAFT, HTH, C-HTH, C-HTC process and boiler combustion process.

[0384] (8) The utility model pulps the biomass organic raw material feed according to industrial standards through the first unit Fenton fly ash zeolite-based catalytic reaction; at the same time, the heavy metal-containing or unsuitable organic pulp is excluded from the processing link of the fertilizer intermediate product, and is used as an additive in the production of catalytic combustion-supporting and oxygen-carrying fuels. Wet biomass refers to plant biomass formed by photosynthesis, including but not limited to biomass waste formed in the past: agricultural and forestry waste, agricultural product processing scraps, poultry and livestock manure, kitchen waste, organic components in peat (peat contains more than 60% lignin), etc.; the debris composed of plants and other biomass is the largest biological renewable resource on the earth (on the order of 100 billion tons / year); taking only a very small part of it for the production of "artificial humic acid" is enough to compensate for the annual loss of global soil organic carbon. BRIEF DESCRIPTION OF THE DRAWINGS

[0385] Figure 1 It is a structural schematic diagram of the processing system of the utility model;

[0386] Figure 2 The utility model is a process flow chart for large-scale production of humic acid zeolite-based nutrient slow-release fertilizer by the treatment system.

[0387] Figure 3 The utility model is a process flow chart for large-scale production of humic acid zeolite-based nutrient slow-release fertilizer by the treatment system.

[0388] Figure 4 The chemical properties of humic substances;

[0389] Figure 5 The hydrogen-carbon ratio, oxygen-carbon ratio, and fuel calorific value diagrams for lignite, peat, and lignocellulosic materials.

[0390] Figure 6 This is the flow chart of the hydrothermal reaction of FA-HTZ fly ash alkali melting.

[0391] Figure 7 The present invention is a production flow chart of humic acid ultra-high efficiency slow-release fertilizer by synergistically coupling the treatment system of the present invention with a 330,000-kilowatt power production system. DETAILED DESCRIPTION

[0392] The following will further describe the utility model in detail in conjunction with the implementation scheme of the production line. It should be understood that the following examples are only for illustrative purposes and explanation of the utility model, and should not be interpreted as limiting the scope of protection of the utility model. All technologies implemented based on the above content of the utility model are included in the scope of protection intended by the utility model.

[0393] Example 1

[0394] Reference Figure 1, a humic acid ultra-high efficiency slow-release fertilizer processing system that is synergistically coupled with a 330,000-kilowatt power production system, including:

[0395] A first unit 3 for separating modified lignin from humic acid-like substances;

[0396] A second unit 4 located downstream of the first unit 3 and used for converting the modified lignin of the first unit 3 into artificial humic acid;

[0397] A third unit 5 located downstream of the second unit 4 and used for catalyzing hydrothermal humification to synthesize artificial humin;

[0398] a fourth unit 6 located downstream of the third unit 5 and used for catalytic hydrothermal carbonization; and

[0399] A fifth unit 1 is located upstream of the first unit 3 and is used to prepare additives in the first unit 3 and / or the third unit 5 and / or the fourth unit 6.

[0400]

Unit 5.1

[0401] The fifth unit 1 is used to prepare the additives in the first unit 3 and / or the third unit 5 and / or the fourth unit 6, for example, the solid acid catalyst is prepared by fly ash alkali melting hydrothermal zeolite (FA-HTZ).

[0402] The unit 1○ includes a polymerization reactor, a grinding device, a dilution tank, an ultrasonic device and a hydrothermal activation device which are connected in sequence.

[0403] The polymerization reactor is provided with a fly ash inlet and an alkaline reagent inlet.

[0404] The unit 1○ also 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 medium liquid obtained by filtration.

[0405] The additive is prepared by using fly ash as raw material through a fusion-hydrothermal double-stage alkali conversion method.

[0406] The preparation method of the additive comprises the following steps: fly ash is melted under alkaline conditions (also known as "alkali melting"), the obtained polymer is ground, diluted, ultrasonically treated, and subjected to hydrothermal activation reaction to obtain the oxygen carrier.

[0407] The alkaline condition can be provided by a strong base, for example, the strong base is potassium hydroxide and / or sodium hydroxide.

[0408] The conditions for the fusion polymerization include: a temperature of 400-650° C. and a time of 2-8 hours; for example, a temperature of 450-550° C. and a time of 4-6 hours.

[0409] The polymer was ground to 0.075 mm to 0.2 mm.

[0410] The concentration of the solid matter in the diluted mixture is 1-5 mol / L, for example 2.5 mol / L.

[0411] The diluent used for dilution is water or the liquid medium recovered from the hydrothermal activation reaction.

[0412] The dilution may or may not be performed with the addition of fly ash.

[0413] The ultrasonic treatment time is 10-30 min, for example 15 min.

[0414] The conditions of the hydrothermal activation reaction include: temperature of 70-100° C., time of 2-8 h; for example, temperature of 80-90° C., time of 4-8 h.

[0415] Alternatively, the preparation method of the additive comprises the following steps: the fly ash is subjected to a two-stage synthesis zeolite process of double-stage fusion (melting and hydrothermal) to prepare the nanocomposite zeolite material.

[0416] The process of the melting stage includes: mixing fly ash with alkali, heating and melting, grinding, and diluting to obtain a crystallization precursor solution.

[0417] Wherein, the base is selected from a strong base, such as sodium hydroxide.

[0418] The heating and melting process may be performed at a temperature of 500 to 600° C. and for a time of 1 to 9 hours.

[0419] The process of the hydrothermal stage includes: aging and hydrothermal process to obtain crystals; or includes: adding doping elements, aging and hydrothermal process to obtain crystallized composite element crystals.

[0420] 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.

[0421] Doping elements are added, preferably before the hydrothermal process with N>1 is started, to introduce designated elements so that these elements uniformly form highly active catalytic sites.

[0422] The doping elements are introduced through the following dopants, including but not limited to nanoparticles, alkaline substances and / or crystal nuclei of the one, two or more doping elements.

[0423] 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:

[0424] When N=1, the crystal precursor solution is obtained by mixing fly ash with alkali, or further mixing with dopants, heating and melting, grinding, and diluting;

[0425] When N≥2, the crystallization precursor solution is obtained by mixing and diluting the filtrate and dopant obtained after the previous hydrothermal crystallization stage, with or without adding alkali as needed.

[0426] The mass ratio of the dopant to the crystallization precursor solution is 1:(1-5), for example, 1:1, 1:2, 1:3, 1:4 or 1:5.

[0427] The temperature of the hydrothermal process is 90-170°C and the time is 2-48 hours.

[0428] The solid acid catalyst can be the fly ash zeolite-based composite nano oxygen carrier described in Chinese patent application 202311217726.6.

[0429] The fly ash is a tiny ash particle discharged during the combustion of fuel, which may or may not contain unburned carbonaceous particles, and is also called fly ash or smoke ash including unburned carbonaceous particles. 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 ultrafine powder raw materials prepared from fly ash from fly ash landfills and boiler combustion residues; preferably, the fly ash generated immediately by the pulverized coal boiler of the power plant is selected, and preferably the fly ash collected by the dust collector at the rear end of the coal-fired boiler is selected.

[0430] The oxygen carrier is prepared from fly ash. Preferably, the oxygen carrier is an oxygen carrier with a dual-phase catalytic function used in a novel chemical looping combustion.

[0431] The oxygen carrier comprises a metal oxide and a carrier, wherein 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, the metal oxide is uniformly distributed (or dispersed) in the crystal structure of the carrier.

[0432] It should be understood by those skilled in the art that when a dispersant is used, the dispersant may be selected from dispersants known to those skilled in the art, as long as it helps to disperse the metal oxide in the support.

[0433] The oxygen carrier has the crystal structure of FAU zeolite.

[0434] 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, aluminum oxide; as an example, the metal oxide is ferric oxide, zinc oxide, aluminum oxide.

[0435] When the metal oxide is ferric oxide, it may have a nanocrystalline particle structure of γ-Fe2O3, α-Fe2O3, or γ-Fe3O4.

[0436] The metal of the metal oxide comes from the metal contained in the fly ash itself, or from an 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.

[0437] Those skilled in the art should understand that when the treatment system is started, metal or metal oxide can be added to the fly ash in the fifth unit 1 as needed so that the solid acid catalyst has 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, there is no need to add additional metal or metal oxide. For this purpose, the first unit 3, the second unit 4, the third unit 5, the fourth unit 6, and the fifth unit 1 of the treatment system of the utility model are each closed, and the connecting pipelines between the first unit 3, the second unit 4, the third unit 5, the fourth unit 6, and the fifth unit 1 are closed to reduce or avoid unnecessary consumption of metal elements.

[0438] 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.

[0439] The metal oxide nanoparticles are ferric oxide nanoparticles with a particle size of 3-5 nm.

[0440] The particle shape of the metal oxide can be round, ellipsoidal or other regular or irregular shapes.

[0441] The oxygen carrier is a micro-nano material, that is, has a micro-nano crystal structure.

[0442] The mass ratio of the metal oxide to the oxygen carrier is 5-35wt%, for example, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%.

[0443] The particle size of the oxygen carrier is 0.075 mm to 0.2 mm, for example, 100 μm, 120 μm, 150 μm, or 180 μm.

[0444] The oxygen carrier is prepared from fly ash as raw material through a fusion polymerization (melt polymerization)-hydrothermal double-stage alkali conversion method.

[0445] The oxygen carrier also 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 with or compensate for the functions of these metal elements.

[0446] The metal element of the metal complex can be selected from rare earth metal elements and / or semi-metal elements; for example, the rare earth metal element is lanthanum (La) or cerium (Ce), preferably cerium; for example, the semi-metal element is silicon (Si).

[0447] The metal complex 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, and titanium, preferably compounds of aluminum and zinc, and more preferably aluminum oxide and zinc oxide.

[0448] In one embodiment, the rare earth metal element is derived from its salt or oxide, and the semi-metal element is derived from its oxide (eg, silicon dioxide).

[0449] In one embodiment, the metal compound is the corresponding metal salt or oxide.

[0450] The metal complex is a nano-scale metal oxide, such as nano-cerium oxide, nano-aluminum oxide and / or nano-zinc oxide.

[0451] 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 further preferably less than 30 nm, 10 nm, or 4 nm.

[0452] The oxygen carrier may further include an additive. For example, the additive is one or more of an inorganic acid, an inorganic base, etc. For example, 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.

[0453] 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, which can improve the combustion efficiency.

[0454] The solid acid catalyst can be a nanocomposite zeolite material described in Chinese patent application 202310381676.9.

[0455] The nano-scale crystal structure of the nano-composite zeolite material is a FAU / Zeolite structure, preferably a FAU / Zeolite Y structure.

[0456] The nanocomposite zeolite material has micro-mesoporous cage void space.

[0457] The nano composite zeolite material is aluminosilicate hydrate.

[0458] The nanocomposite zeolite material further comprises one, two or more of the following elements: magnesium (Mg), iron (Fe), zinc (Zn), molybdenum (Mo), boron (B), selenium (Se), etc. Preferably, the elements are added to the nanocomposite zeolite material in the form of their chlorides (e.g. zinc chloride, iron chloride) as raw materials.

[0459] The nanocomposite zeolite material is a Fugarst zeolite type structure (FAU).

[0460] The nanocomposite zeolite material has a three-level pore structure: the pore diameter of the first-level pore structure does not exceed 10nm, for example, does not exceed 5nm, and is preferably less than 2nm (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 50nm; the pore diameter of the third-level pore structure (also called macropores) is greater than 50nm, for example, greater than 50nm and not more than 500nm, such as 200nm.

[0461] The sum of the specific surface areas of the nanocomposite zeolite material is 150 to 1500 m 2 / g, for example 300~1200m 2 / g, such as 500~1000m 2 / g.

[0462] The cation exchange capacity (CEC) of the nanocomposite zeolite material is 150-250 cmol (+) / kg.

[0463] The pore volume of the nanocomposite zeolite material accounts for more than 50%, such as more than 60%, such as 65-80%.

[0464] The mass density of the nanocomposite zeolite material is 2.1-2.2 g / cc.

[0465] The nanocomposite zeolite material has water holding performance (water holding performance 50 wt%).

[0466] The nanocomposite zeolite material is insoluble in water at any pH. Alternatively, the nanocomposite zeolite material has the characteristics of being resistant to acid and alkali, that is, it is neither soluble in alkali (high pH) nor in acid (low pH).

[0467] 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.), and ultrafine powder raw materials prepared from fly ash from fly ash landfills and boiler combustion residues; preferably, fly ash generated immediately by the pulverized coal boiler of the power plant is selected, and preferably fly ash collected by the dust collector at the rear end of the coal-fired boiler is selected.

[0468] After the hydrothermal activation reaction is completed, the product is filtered, washed, and dried to obtain the additive (such as oxygen carrier). The solid acid catalyst fly ash zeolite-based material synthesized by the fifth unit 1 is used as a macronutrient (such as K + or NH4 + 、NO3 - ) is a slow-release carrier that releases nutrient cations and exchanges Na in soil water in sequence. + , Ca 2+ The special function of cations such as zeolite, the macronutrients loaded only follow the inherent preference order of cation exchange of zeolite structure, slowly releasing nutrients, cation exchange and absorbing Na + or Ca 2+ , reducing soil salinization; fly ash synthesized zeolite-based materials, with their unique honeycomb micro-mesoporous cage structure, disperse and support beneficial mineral elements, providing energy and mineral elements for soil microorganisms; when widely used in soil as a fertilizer slow-release medium, it can promote soil microecological balance, promote the degradation or inactivation of soil toxic substances, and achieve the effects of promoting plant growth and improving soil.

[0469] The fly ash synthesized zeolite substrate can also be used as the solid acid catalyst of the fourth unit 6, i.e., catalytic hydrothermal carbonization; in the C-HTC liquid phase reaction of the coal fuel pretreatment of the third unit 5, it can catalyze the carbon conversion rate of the hydrothermal pretreatment process.

[0470]

Unit 6.2

[0471] In one embodiment of the present invention, the system further comprises a sixth unit 2 for pulping raw materials containing lignin such as peat, lignite and wet biomass.

[0472] The sixth unit 2 is a wet biomass processing pulping unit, which is used to pulp feed materials containing lignin components such as peat, lignite and wet biomass.

[0473] In one embodiment of the present invention, the system further comprises a sixth unit 2' for auxiliary pulping processing of wet biomass materials that cannot be used as agricultural fertilizers, such as municipal sludge and other organic sludges including heavy metal pollution.

[0474] In one embodiment of the utility model, the sixth unit 2 and the sixth unit 2' are located at the feed end of the bulk organic materials such as lignite and peat upstream of the production process, so as to pulp the organic materials containing lignin components according to industrial standards; at the same time, the heavy metal-containing or unsuitable organic pulp is removed from the fertilizer product processing link, and the auxiliary pulping processing sixth unit 2' is used to pulp the additives for the production of catalytic combustion-supporting and oxygen-carrying fuel auxiliary raw materials.

[0475] In one embodiment of the present invention, the sixth unit 2 is provided with a feed inlet for peat, lignite and other raw materials rich in lignocellulose.

[0476] In one embodiment of the present utility model, the sixth unit 2 is provided with a discharge port for the single-water coal slurry.

[0477] In one embodiment of the present invention, the sixth unit 2' is provided with a feed inlet for municipal sludge or other organic sludge containing excessive heavy metals.

[0478] In one embodiment of the present invention, the sixth unit 2' is provided with a discharge port for the municipal sludge homogenate.

[0479]

Unit 1, Part 3

[0480] The first unit 3 is used to use additives as CAFT (Catalytic Alkli Fenton Treatment) reaction catalytic materials to strengthen the high-density free radical liquid phase reaction incorporated into the lignin particles, quickly form an aggregation pattern of amphiphilic groups, and separate modified lignin similar to humic acid substances that can stimulate plants to produce tolerance to salt-induced abiotic stress.

[0481] The first unit 3 comprises a Fenton reaction slurry mixing device, a microwave device and an extraction device which are connected in sequence.

[0482] The Fenton reaction slurry mixing device is provided with a biomass raw material inlet, an additive inlet and an alkaline reagent inlet.

[0483] The biomass raw material is selected from organic waste that is cleaned before combustion of traditional boiler fuels (including low-value lignite, peat, and biomass).

[0484] The alkaline agent may be provided by a strong base, for example, the strong base is potassium hydroxide and / or sodium hydroxide.

[0485] A solid-liquid separation device, such as a centrifuge, is also 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.

[0486] 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.

[0487] 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.

[0488] The first unit 3 also includes a filtering device, the inlet of which is connected to the outlet of the extraction device; the liquid outlet of the filtering device is connected to the third unit 5 through a pipeline, so that the water-carbon slurry obtained by filtration is reused.

[0489] The product of the first unit 3 is a modified lignin aqueous slurry comprising fulvic acid liquid, humic acid liquid and Fenton pulp, which can stimulate plants to produce humic acid-like substances that are tolerant to salt-induced abiotic stress.

[0490] The product of the first unit 3 can be filtered by pressure to prepare a modified lignin water slurry similar to a humic acid substance.

[0491] The first unit 3 may further include a storage device for storing the obtained humic acid product.

[0492] The additive is prepared through unit ○1.

[0493]

Unit 2.4

[0494] The second unit 4 is used to catalyze a hydrothermal humification (HTH) reaction to efficiently convert biomass into artificial humic acid materials.

[0495] The second unit 4 includes a catalytic hydrothermal humification device.

[0496] The second unit 4 may also include a feeding device to provide reaction substrates for the catalytic hydrothermal humification device. For example, the feeding device is a feeding device for solid-liquid mixed materials.

[0497] The solid-liquid mixed material contains organic carbon.

[0498] The second unit 4 can be used to process organic carbon-containing materials, such as water carbon slurry produced by the first unit 3.

[0499] The second unit 4 may further include a steam generating device to provide the catalytic hydrothermal humification device with steam required for the hydrothermal humification reaction.

[0500] The second unit 4 also includes a spiral flow controller to promote the reaction in the catalytic hydrothermal humification device.

[0501] The catalytic hydrothermal humification device is preferably a horizontal tube reaction device.

[0502] 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.

[0503] A hydrothermal humification product separation device is also 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.

[0504] A hydrothermal humification gas phase treatment device is also 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.

[0505] 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.

[0506] 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.

[0507] 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.

[0508] 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.

[0509] 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.

[0510] The hydrothermal humification solid-liquid-gas mixture material comprises a mixture of solid material, liquid material and gas material.

[0511] A solid-liquid separation device, such as a centrifuge, is also 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 that the hydrothermal humification solid-phase material and the hydrothermal humification liquid-phase material in the hydrothermal humification solid-liquid-gas mixture are separated.

[0512] 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.

[0513] 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.

[0514] 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.

[0515] As an example, 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.

[0516] 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.

[0517] The second 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.

[0518] The second unit 4 further includes one or more conveying devices to convey one, two or three of the gas phase material, solid phase material and gas phase material mentioned above to the corresponding device of the first unit 3 for processing. Preferably, such a conveying device can be arranged between every two devices. It should be understood by those skilled in the art that such a conveying device is known in the art, and for this reason, the utility model does not particularly limit the specific structure of the conveying device, as long as it can effectively convey the material to the desired device.

[0519] When the material needs to be cooled, circulating water can be selected for cooling. For this reason, the cooling device of the utility model can also be provided with a pipeline for circulating cooling water.

[0520] The reaction temperature in the catalytic hydrothermal humification device may be about 150-230° C., such as 180-200° C.; the reaction time may be about 30-300 min, such as 60-120 min.

[0521] The product of the second unit 4 comprises humic acid liquid and humin slurry.

[0522] The product of the second unit 4 can be passed through filter pressing, drying and / or granulation devices to efficiently convert the biomass into a humus-like polymer artificial humic acid material.

[0523] The second unit 4 may further include a storage device for storing the obtained humin slurry, humic acid composite zeolite-based synthetic material and humic acid liquid product.

[0524]

Unit 3-5

[0525] The third unit 5 is used for catalyzing the hydrothermal humification (C-HTH) reaction to produce humin.

[0526] The third 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.

[0527] 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 be directly processed by the catalytic hydrothermal humification device.

[0528] Those skilled in the art should understand that the catalytic hydrothermal humification device disposed downstream of the depolymerization device as described herein may include not only a method of directly subjecting the material output from the depolymerization device to treatment by the catalytic hydrothermal humification device, but may also include a method of directly subjecting the material to treatment by the catalytic hydrothermal humification device, or subjecting the material output from the depolymerization device to treatment by first other devices and then by the catalytic hydrothermal humification device. The above-mentioned different methods should all be understood as optional methods covered by "the catalytic hydrothermal humification device disposed downstream of the depolymerization device". Therefore, the depolymerization device may be directly connected to the catalytic hydrothermal humification device or not.

[0529] A buffer separation device and / or other devices may be provided between the depolymerization device and the downstream catalytic hydrothermal humification device. For example, when the depolymerization device is not directly connected to the catalytic hydrothermal humification device, the material output from the depolymerization device may be first processed by the buffer separation device or other devices, and then processed by the catalytic hydrothermal humification device.

[0530] The buffer separation device may be a gas-liquid buffer separator, such as a gas-liquid buffer separator known to those skilled in the art.

[0531] The third unit 5 may also include a feeding device to provide reaction substrates for the depolymerization device. For example, the feeding device is a feeding device for a solid-liquid mixture.

[0532] The solid-liquid mixed material contains organic carbon.

[0533] The third unit 5 can be used to process materials containing organic carbon, such as humin slurry, municipal garbage (organic solid waste), wet biomass, etc. For example, the material containing organic carbon can be selected from one or a mixture of two or more materials containing organic carbon, such as humin slurry, wet biomass slurry without municipal sludge, municipal garbage, domestic garbage, restaurant kitchen waste, kitchen waste, municipal feces, sewage treatment sludge, water body sediment, garbage leachate, wood waste residue, crop straw, peat, lignite, bituminous coal, etc.

[0534] For example, when the material containing organic carbon is selected from domestic garbage, restaurant garbage, kitchen waste, municipal feces, sewage treatment sludge, water body sediment, garbage leachate, wood waste residue, crop straw, etc., it can be first depolymerized and then catalytically carbonized. Alternatively, when the material containing organic carbon is selected from humin slurry, wet biomass homogenate without municipal sludge, peat, lignite, bituminous coal, etc., it can be directly catalytically carbonized.

[0535] The depolymerization device may be provided with at least one feed inlet, so that the material provided by the feed device can enter the depolymerization device.

[0536] The material in the feeding device can directly enter the depolymerization device. Alternatively, as another option, a raw material mixer, a preheating mixer and / or a mixing liquid storage tank are arranged 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 liquid storage tank before entering the depolymerization device.

[0537] The third unit 5 may further include a steam generating device to provide the depolymerization device with steam required for the depolymerization reaction.

[0538] The steam generating device can also provide the catalytic hydrothermal humification device with steam required for the hydrothermal humification reaction.

[0539] The depolymerization device may be provided with at least one air inlet so that the steam in the steam generating device can enter the depolymerization device.

[0540] The depolymerization device may also be provided with at least one additive feed port, so that the additives required for the depolymerization reaction can enter the depolymerization device.

[0541] Alternatively, as another option, the additive may also enter the depolymerization device through the feed port of the solid-liquid mixture, as long as it can participate in the depolymerization reaction.

[0542] The depolymerization device may also be provided with at least one outlet for depolymerization gas phase material and at least one outlet for depolymerization non-gas phase material.

[0543] Preferably, the depolymerized gaseous material comprises tail gas generated by the depolymerization reaction, and the depolymerized non-gaseous material comprises a mixture of solid-phase material and liquid-phase material which needs to be further processed in a buffer separation device and / or a catalytic carbonization device after being processed by a depolymerization device.

[0544] 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 phase gas cooling device and / or a first gas phase purification device, preferably including a first phase cooling device and a first gas phase purification device.

[0545] The condensate obtained by cooling the depolymerized 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.

[0546] The depolymerization gas phase treatment device may be connected to a discharge device, so that the gas obtained after being treated by the depolymerization gas phase treatment device enters the discharge device for discharge.

[0547] The third unit 5 further comprises a spiral flow controller to promote the reaction in the depolymerization device and / or the catalytic hydrothermal humification device.

[0548] The depolymerization device and / or the catalytic hydrothermal humification device is preferably a horizontal tube reaction device.

[0549] 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.

[0550] A hydrothermal humification product separation device is also 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.

[0551] A hydrothermal humification gas phase treatment device is also 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.

[0552] 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.

[0553] 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.

[0554] 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.

[0555] 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.

[0556] 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.

[0557] The hydrothermal humification solid-liquid-gas mixture material comprises a mixture of solid material, liquid material and gas material.

[0558] A solid-liquid separation device, such as a centrifuge, is also 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 that the hydrothermal humification solid-phase material and the hydrothermal humification liquid-phase material in the hydrothermal humification solid-liquid-gas mixture are separated.

[0559] 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.

[0560] 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.

[0561] 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.

[0562] As an example, 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.

[0563] 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.

[0564] The hydrothermal humification system 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 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.

[0565] The water-water thermal humification system also includes one or more conveying devices to convey one, two or three of the gas phase materials, solid phase materials and gas phase materials mentioned above to the corresponding devices in the water-water thermal humification system for treatment. Preferably, such a conveying device can be set between every two devices. Those skilled in the art should understand that such a conveying device is known in the art, and for this reason, the utility model does not particularly limit the specific structure of the conveying device, as long as it can effectively convey the material to the desired device.

[0566] When the material needs to be cooled, circulating water can be selected for cooling. For this reason, the cooling device of the utility model can also be provided with a pipeline for circulating cooling water.

[0567] The temperature for depolymerization of 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.

[0568] The reaction temperature in the catalytic hydrothermal humification device may be about 150-230° C., such as 180-200° C.; the reaction time may be about 30-300 min, such as 60-120 min.

[0569] The third unit 5 may also include one, two or more pre-treatment devices for pre-treating the organic carbon-containing material before depolymerization (or referred to as "pre-treatment"). For example, the pre-treatment includes but is not limited to pre-treating the organic carbon-containing material by crushing, pulping, depolymerization, extraction, soaking, etc.

[0570] The additive may be an additional additive required for any device in the third unit 5 to react or process, such as one or more of a pH regulator, a catalyst, etc. For example, the additive is prepared by unit 1○.

[0571] Each device in the third unit 5 may be optionally independently provided with a feed port for feeding additives. 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 is mixed with the additive in the depolymerization reaction device for reaction.

[0572] The additive is a dispersion in which a zeolite-based carrier is used and a metal oxide is primarily dispersed in the zeolite-based carrier.

[0573] 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 zeolite-based primary dispersion of the additive is further dispersed in water coke for a secondary time.

[0574] The weight ratio of the raw material containing organic carbon 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.

[0575] 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 to 180°C, such as 170°C on average; and / or, the reaction time of the depolymerization device and / or the catalytic hydrothermal humification device can be reduced to 30 to 120 min, for example, 20 to 60 min.

[0576] The product of the third unit 5 includes humin slurry, humic acid composite zeolite-based synthetic material and humic acid liquid.

[0577] The product of the third unit 5 can be filtered, dried and / or granulated to prepare a composition containing modified water char, humic acid and / or organic carbon medium nutrients that can be widely used in soil fertilizer, promoting the ecological balance of soil microorganisms and soil animals, promoting the degradation or inactivation of toxic substances in the soil, improving soil pH, plant fertilizer, promoting plant growth, plant irrigation, etc., and can achieve good results.

[0578] The third unit 5 may also include a storage device for storing the obtained humin slurry, humic acid composite zeolite-based synthetic material and humic acid liquid product.

[0579] The third unit 5 can be modified and adjusted by solid acid catalysis in any chemical direction, and can also be used to treat high-salt and low-salt reaction materials at the same time. Biomass raw materials have a significant effect of accelerating humification under the action of solid acid catalytic materials. Under solid acid catalytic conditions, humin can be converted into a carbon compound with a sponge-like structure, namely modified water coke, which has similar performance to natural humin and can provide the required energy and mineral requirements for soil microorganisms and soil animals. The mixture of modified water coke and soil humus can more stably or effectively assist the degradation or inactivation of toxic substances in the soil; the composition of modified water coke combined with humus substances and / or organic carbon medium nutrients prepared by the third unit 5 can buffer soil pH, release carbon dioxide, and play a role in buffering soil hydrogen ion concentration; and can be widely used in soil fertilizer, 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 fertilizer, promoting plant growth, plant irrigation, etc., and can achieve good results.

[0580]

Unit 4.6

[0581] The fourth unit 6 is used for catalytic hydrothermal carbonization (C-HTC for short).

[0582] The fourth unit 6 includes a catalytic carbonization device, or includes a depolymerization device and a catalytic carbonization device disposed downstream of the depolymerization device.

[0583] 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 be directly processed by the catalytic carbonization device.

[0584] The method of placing the catalytic carbonization device downstream of the depolymerization device as described herein may include not only a method of directly subjecting the material produced by the depolymerization device to treatment by the catalytic carbonization device, but also a method of directly subjecting the material to treatment by the catalytic carbonization device, or subjecting the material produced by the depolymerization device to treatment by other devices first and then by the catalytic carbonization device. The above different methods should all be understood as optional methods covered by "the catalytic carbonization device is placed downstream of the depolymerization device". Therefore, the depolymerization device and the catalytic carbonization device may be directly connected or not directly connected.

[0585] A buffer separation device and / or other devices may be provided between the depolymerization device and the downstream catalytic carbonization device. For example, when the depolymerization device is not directly connected to the catalytic carbonization device, the material output from the depolymerization device may be first processed by the buffer separation device or other devices, and then processed by the catalytic carbonization device.

[0586] The buffer separation device may be a gas-liquid buffer separator, such as a gas-liquid buffer separator known to those skilled in the art.

[0587] 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 mixture.

[0588] The solid-liquid mixed material contains organic carbon.

[0589] The fourth unit 6 can be used to process slurries containing organic carbon materials, such as humin slurries, municipal garbage (organic solid waste), wet biomass and other pulping slurries. For example, the material containing organic carbon can be selected from humin slurries, municipal sludge leachate, municipal garbage, domestic garbage, restaurant kitchen waste, kitchen waste, municipal feces, sewage treatment sludge, water body sediment, garbage leachate, wood waste, crop straw, peat, lignite, bituminous coal and other material slurries containing organic carbon, or a mixture of two or more slurries.

[0590] For example, when the material containing organic carbon is selected from domestic garbage, restaurant garbage, kitchen waste, municipal feces, sewage treatment sludge, water body sediment, garbage leachate, wood waste residue, crop straw, etc., it can be pulped and depolymerized first, and then catalytically carbonized. Alternatively, when the material containing organic carbon is selected from humin slurry, peat, lignite, bituminous coal slurry, etc., it can be directly catalytically carbonized.

[0591] The depolymerization device may be provided with at least one feed inlet, so that the slurry made from the material provided by the feed device can enter the depolymerization device.

[0592] The material in the feeding device can be directly fed into the depolymerization device after being slurried. Alternatively, as another option, a mixer for slurrying raw materials, a preheating mixer and / or a mixing liquid storage tank are arranged 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 liquid storage tank before entering the depolymerization device.

[0593] The hydrothermal carbonization system may further include a steam generating device to provide the depolymerization device with steam required for the depolymerization reaction.

[0594] The steam generating device can also provide the catalytic carbonization device with steam required for the carbonization reaction.

[0595] The depolymerization device may be provided with at least one air inlet so that the steam in the steam generating device can enter the depolymerization device.

[0596] The depolymerization device may also be provided with at least one additive feed port, so that the additives required for the depolymerization reaction can enter the depolymerization device.

[0597] Alternatively, as another option, the additive may also enter the depolymerization device through the feed port of the solid-liquid mixture, as long as it can participate in the depolymerization reaction.

[0598] The depolymerization device may also be provided with at least one outlet for depolymerization gas phase material and at least one outlet for depolymerization non-gas phase material.

[0599] Preferably, the depolymerized gaseous material comprises tail gas generated by the depolymerization reaction, and the depolymerized non-gaseous material comprises a mixture of solid-phase material and liquid-phase material which needs to be further processed in a buffer separation device and / or a catalytic carbonization device after being processed by a depolymerization device.

[0600] 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 phase gas cooling device and / or a first gas phase purification device, preferably including a first phase cooling device and a first gas phase purification device.

[0601] The condensate obtained by cooling the depolymerized gas phase material can be mixed with the material provided by the feeding device to form a slurry, for example, it can be mixed with the material provided by the feeding device to form a slurry in a raw material mixer.

[0602] The depolymerization gas phase treatment device may be connected to a discharge device, so that the gas obtained after being treated by the depolymerization gas phase treatment device enters the discharge device for discharge.

[0603] The fourth unit 6 further comprises a spiral flow controller to promote the reaction in the depolymerization device and / or the catalytic carbonization device.

[0604] The depolymerization device and / or catalytic carbonization device is preferably a horizontal tube reaction device.

[0605] The catalytic carbonization device is provided with at least one air inlet so that the steam in the steam generating device can enter the catalytic carbonization device.

[0606] A carbonization product separation device is also provided downstream of the catalytic carbonization device to separate gaseous materials from non-gaseous materials in the materials produced by the catalytic carbonization device.

[0607] A carbonized gas phase treatment device is also provided downstream of the carbonized product separation device. The carbonized 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.

[0608] 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 mixture 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.

[0609] The carbonized solid-liquid-gas mixture material outlet of the catalytic carbonization device is connected to the inlet of the carbonization product separation device.

[0610] The carbonized product separation device is provided with at least one carbonized gas phase material outlet and at least one carbonized solid-liquid-gas mixture 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.

[0611] The condensate obtained by cooling the carbonized gas phase material can be mixed with the material provided by the feed device, for example, it can be mixed with the material provided by the feed device in the raw material mixer. Therefore, the carbonized gas phase processing device can be connected to the raw material mixer through a liquid phase delivery pipeline.

[0612] The carbonized 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 carbonized gas phase treatment device enters the discharge device for discharge.

[0613] The carbonized solid-liquid-gas mixture material comprises a mixture of solid material, liquid material and gas material.

[0614] 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 mixture 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 mixture.

[0615] The solid-liquid separation device is provided with at least one carbonized solid phase material outlet to provide a carbonized solid phase product.

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

[0617] 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 carbonized 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.

[0618] As an example, 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.

[0619] 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.

[0620] The hydrothermal carbonization system 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 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.

[0621] The hydrothermal carbonization system further includes one or more conveying devices to convey one, two or three of the gas phase material, solid phase material and gas phase material mentioned above to the corresponding device in the hydrothermal carbonization system for processing. Preferably, such a conveying device can be arranged between every two devices. It should be understood by those skilled in the art that such a conveying device is known in the art, and for this reason, the utility model does not particularly limit the specific structure of the conveying device, as long as it can effectively convey the material to the desired device.

[0622] When the material needs to be cooled, circulating water can be selected for cooling. For this reason, the cooling device of the utility model can also be provided with a pipeline for circulating cooling water.

[0623] The temperature for depolymerization of 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.

[0624] The reaction temperature in the catalytic carbonization device may be about 150-230° C., such as 180-200° C.; the reaction time may be about 30-300 min, such as 60-120 min.

[0625] The fourth unit 6 may also include one, two or more pre-treatment devices for pre-treating the organic carbon-containing material before depolymerization (or referred to as "pre-treatment"). For example, the pre-treatment includes but is not limited to pre-treating the organic carbon-containing material by crushing, pulping, depolymerization, extraction, soaking, etc.

[0626] The additive may be an additional additive required for any device in the fourth unit 6 to react or process, such as one or more of a pH regulator, a catalyst, etc. For example, the additive is prepared by unit 1○.

[0627] Each device in the fourth unit 6 may be optionally independently provided with a feed port for feeding additives. 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 is mixed with the additive in the depolymerization reaction device for reaction.

[0628] The additive is a dispersion in which a zeolite-based carrier is used and a metal oxide is primarily dispersed in the zeolite-based carrier.

[0629] 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 zeolite-based primary dispersion of the additive is further dispersed in water coke for a secondary time.

[0630] The weight ratio of the raw material containing organic carbon 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.

[0631] 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 carbonization device can be reduced to an average of 150 to 180°C, such as 170°C; and / or, the reaction time of the depolymerization device and / or the catalytic carbonization device can be reduced to 30 to 120 min, for example, 20 to 60 min.

[0632] The product of the fourth unit 6 is a water coke slurry containing the additive (such as a solid acid catalyst, preferably, the content of the solid acid catalyst is higher than 20%).

[0633] The product of the fourth unit 6 can be passed through a filter press, drying and / or pelletizing device to prepare a water coke fuel product. Preferably, the particle size of the water coke fuel product of the fourth unit 6 can be adjusted to make it suitable for the requirements or standards of subsequent units.

[0634] The method may further include a storage device for storing the obtained water coke fuel product.

[0635] The fourth unit 6 in the utility model 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 fuel. The catalytically carbonized modified water coke is also a biomass energy fuel with high cleanliness and good gasification effect.

[0636] Example 2

[0637] Reference Figure 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 of Example 1, specifically comprising the following steps:

[0638] (1) Using fly ash as raw material, preparing in the fifth unit 1 an additive for preparing the first unit 3 and / or the third unit 5 and / or the fourth unit 6;

[0639] (2) Under the action of the additive prepared in the fifth unit 1, the lignin pulp is subjected to the CAFT humification heterogeneous catalytic Fenton reaction first unit 3 to separate the modified lignin similar to humic acid (such as Fenton catalytic modified lignin pulp);

[0640] (3) The modified lignin produced by the first unit 3 is converted into artificial humic acid liquid and humin slurry in the second unit 4;

[0641] (4) Under the action of the additive prepared in the fifth unit 1, the humin slurry produced by the second unit 4 and the wet biomass homogenate without municipal sludge are subjected to hydrothermal humification in the third unit 5 to synthesize artificial humin, humic acid composite zeolite-based synthetic material and humic acid liquid;

[0642] (5) Under the action of the additive prepared in the fifth unit 1, the humin slurry produced by the third unit 5 and the wet biomass slurry containing municipal sludge are hydrothermally carbonized in the fourth unit 6 to prepare a solid oxygen-carrying carbon-based catalytic combustion-supporting material.

[0643] The fly ash is a tiny ash particle discharged during the combustion of fuel, which may or may not contain unburned carbonaceous particles, and is also called fly ash or smoke ash including unburned carbonaceous particles. In a preferred embodiment, the fly ash is taken from the combustion fly ash produced by the 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 the fly ash landfill and the ultrafine powder raw material prepared from the boiler combustion residue; preferably, the fly ash generated immediately by the pulverized coal boiler of the power plant is selected, preferably the fly ash collected by the dust collector at the rear end of the coal-fired boiler and / or selected from the organic waste cleaned before the combustion of traditional boiler fuel (including low-value lignite, peat, biomass).

[0644] In the humic acid composite zeolite-based synthetic material, the mass ratio of humic acid to fly ash zeolite-based material is 1:2-10:1, for example 1:1-5:1, exemplified by 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1.

[0645] In this embodiment, the output of the humic acid composite zeolite-based synthetic material of the third unit 5 is three times the feed amount of the fly ash material.

[0646] Example 3

[0647] A method for treating fly ash comprises treating fly ash material using the treatment system of Example 1.

[0648] Example 4

[0649] A slow-release fertilizer comprises the humic acid composite zeolite-based synthetic material of Example 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.

[0650] The humic acid composite zeolite-based material prepared by the above-mentioned treatment system can be used as a slow-release fertilizer and as a modifier to comprehensively enhance soil fertility. At a cumulative application rate of no less than 2.5 metric tons per hectare over five years, it can reduce soil ammonia volatilization by more than 50%, increase soil moisture retention by 60%, and increase soil available water storage capacity by 75%.

[0651] The above examples illustrate the specific implementation of the present invention. However, the protection scope of the present invention is not limited to the above-mentioned exemplary implementation. Any modification, equivalent replacement, improvement, etc. made by those skilled in the art within the spirit and principle of the present invention shall be included in the protection scope of the claims of the present invention.

Claims

1. A system comprising: A first unit (3) for separating modified lignin from humic acid-like substances; A second unit (4) located downstream of the first unit (3) and used for converting the modified lignin of the first unit (3) into artificial humic acid; A third unit (5) located downstream of the second unit (4) and used for catalyzing hydrothermal humification to synthesize artificial humin; a fourth unit (6) located downstream of the third unit (5) and used for catalytic hydrothermal carbonization; and A fifth unit (1) is located upstream of the first unit (3) and is used to prepare additives in the first unit (3) and / or the third unit (5) and / or the fourth unit (6).

2. The system according to claim 1, characterized in that The fifth unit (1) comprises a polymerization reaction kettle, a grinding device, a dilution tank, an ultrasonic device and a hydrothermal activation device connected in sequence; And / or, the polymerization reactor is provided with a fly ash inlet and an alkaline reagent inlet; And / or, the fifth 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 is recovered and reused.

3. The system according to claim 1, characterized in that The first unit (3) is used to use the additive as a catalytic material for the Fenton reaction in 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; And / or, the first unit (3) comprises a Fenton reaction slurry mixing device, a microwave device and an extraction device connected in sequence; And / or, the Fenton reaction slurry mixing device is provided with a biomass raw material inlet, an additive inlet and an alkaline reagent inlet; And / or, a solid-liquid separation device is further provided downstream of the microwave device, and an outlet of the mixed material of the microwave device is connected to an inlet of the solid-liquid separation device, so as to separate the solid-phase material and the liquid-phase material of the Fenton catalytic reaction in the mixed material of the microwave device; And / or, 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; And / or, 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; And / or, the first 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 third unit (5) via a pipeline, so that the water-carbon slurry obtained by filtration is reused; And / or, the first unit (3) further comprises a storage device for storing the obtained humic acid product.

4. The system according to claim 1, characterized in that The second unit (4) comprises a catalytic hydrothermal humification device; And / or, the second unit (4) further comprises a feeding device; And / or, the second unit (4) further comprises a steam generating device.

5. The system according to claim 4, characterized in that The second unit (4) further comprises a spiral flow controller to promote the reaction in the catalytic hydrothermal humification device; And / or, the catalytic hydrothermal humification device is a horizontal tube reaction device; And / or, the catalytic hydrothermal humification device is provided with at least one air inlet so that the steam in the steam generating device enters the catalytic hydrothermal humification device.

6. The system according to claim 4, characterized in that A hydrothermal humification product separation device is also provided downstream of the catalytic hydrothermal humification device; And / or, 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 includes a second gas phase cooling device and / or a second gas phase purification device; And / or, the catalytic hydrothermal humification 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, and 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; And / or, 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; And / or, 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, and 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; And / or, the hydrothermal humification gas phase treatment device is connected to the raw material mixer via a liquid phase delivery pipeline; And / or, the hydrothermal humification gas phase treatment device is 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.

7. The system according to claim 6, characterized in that A solid-liquid separation device is also provided downstream of the hydrothermal humification product separation device, and the outlet of the hydrothermal humification solid-liquid-gas mixture material is connected to the inlet of the solid-liquid separation device; And / or, the solid-liquid separation device is provided with at least one hydrothermal humification solid phase material outlet; And / or, the solid-liquid separation device is provided with at least one outlet for hydrothermal humification liquid phase material; And / or, a heavy metal separation device is arranged downstream of the solid-liquid separation device, and the heavy metal separation device is a heavy metal physical separation device and / or a heavy metal chemical separation device.

8. The system according to any one of claims 4 to 7, characterized in that: The second 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.

9. The system according to any one of claims 1 to 7, characterized in that: The third 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.

10. The system according to any one of claims 1 to 7, characterized in that: The fourth unit (6) comprises a catalytic carbonization device, or comprises a depolymerization device and a catalytic carbonization device arranged downstream of the depolymerization device.

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