Chemical looping combustion system of fly ash solid waste oxygen-carrying medium and application of chemical looping combustion system in biomass thermoelectric conversion

Abstract

According to the novel biomass thermoelectric conversion fly ash chemical looping boiler system, the functional layout of in-situ production of fly ash zeolite-based catalytic materials in the implementation scheme of the novel biomass thermoelectric conversion fly ash chemical looping boiler system initiates a nanotechnology approach for thermochemical catalytic synergy in the biomass thermoelectric conversion process; the solid waste is regenerated into a catalytic material in situ and value-added circulation of the catalytic material is used in situ is realized, and an oxidation / reduction high-efficiency chemical looping loop for in-situ low-cost production and in-situ high-value application of the solid metal oxide catalyst is constructed; in addition, the fly ash zeolite-based solid acid catalyst with the biphase catalysis function is designed into a single material, so that the complexity of the industrial process is simplified, and the overall cost of the system is reduced.

Description

[0001] This application claims the priority benefit of a prior application filed with the State Intellectual Property Office of China on November 7, 2023, with patent application number 202311472824.4, entitled “Chemical chaining combustion system of fly ash solid waste oxygen-carrying medium and its use in biomass thermal power conversion”. The entire text of the prior application is incorporated into this application by reference. Technical Field

[0002] The present invention relates to a chemical chain combustion system of fly ash solid waste oxygen-carrying medium and its use in biomass thermoelectric conversion, specifically including a technical approach to in-situ resource utilization of fly ash solid waste, and an implementation plan for the application of this technical approach in the improvement and upgrading of traditional boiler combustion systems for biomass thermoelectric conversion. The application of this technical approach to the transformation of traditional boiler combustion systems does not require changing the existing equipment of the traditional boiler combustion system, but directly upgrades the traditional boiler combustion system to an advanced and efficient chemical chain boiler combustion system. The present invention belongs to the field of fly ash solid waste resource utilization and new chemical chain boiler combustion technology for biomass energy. Background Art

[0003] As the "renewable carbon" of the earth, biomass comes from photosynthesis during plant growth. Among them, plant cell walls (also known as "lignocellulose") are the most abundant biomass resources on the earth, with an annual renewable output of more than 170 billion tons. Therefore, the traditional boiler combustion technology of biomass thermal power conversion has always been the mainstream technology of biomass renewable energy in my country.

[0004] Biomass contains a lot of water. When it is heated to the boiling point of water at normal atmospheric pressure, 100°C, the water in the biomass begins to evaporate, consuming a lot of heat energy. Especially in the boiler combustion system of biomass thermal power conversion, the thermochemical reaction of biomass directly entering the boiler combustion atmosphere consumes more than 2 / 3 of its own biomass energy and a lot of water.

[0005] Moreover, boiler combustion will produce a large amount of fly ash, which is a complex of coal ash, mixed coal slag, dust and other sulfates, nitrates and other substances produced during the combustion process. Fly ash is generally fine particles, usually suspended in the flue gas produced by combustion, and can be spread to the surrounding environment through the air. Because it contains a variety of harmful substances, such as heavy metals, dioxins and polycyclic aromatic hydrocarbons, fly ash causes certain harm to the environment and human health. There are reports on the physical and chemical properties of fly ash produced by domestic waste incineration plants. The results show that the mass fraction of fly ash in the grate furnace using pure waste incineration is higher than the mass fraction of fly ash in the fluidized bed incineration using mixed coal, and as the size of fly ash particles decreases, the concentration of heavy metals in fly ash shows an increasing trend. The basic components of fly ash are Ca, Si, Cl, K, Na, S, Al, Mg and Fe, as well as heavy metals such as Zn, Pb, Mn, Cu, Cr, etc.

[0006] Therefore, there is an urgent need to provide efficient, environmentally friendly and cost-controlled biomass-to-energy conversion systems and methods, especially to develop advanced and efficient chemical chain boiler combustion systems without changing the existing equipment of traditional boiler combustion systems. Summary of the invention

[0007] In order to improve the technical problems existing in the traditional biomass thermal power boiler system, the present invention provides a combustion system, comprising:

[0008] Unit A for catalytic hydrothermal carbonization;

[0009] A unit B located downstream of the unit A and used for combustion;

[0010] a unit C located downstream of the unit B and used to prepare the additive in the unit A; and

[0011] The additive produced by unit C is conveyed to the transfer unit D of unit A.

[0012] According to an embodiment of the present invention, the combustion system is a chemical looping combustion system.

[0013] According to an embodiment of the present invention, each unit of the combustion system may independently have the following definitions:

[0014]

Unit A

[0015] According to an embodiment of the present invention, the unit A is used for catalytic hydrothermal carbonization (C-HTC for short).

[0016] According to an embodiment of the present invention, the unit A comprises a catalytic carbonization device, or comprises a depolymerization device and a catalytic carbonization device disposed downstream of the depolymerization device.

[0017] According to an embodiment of the present invention, 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.

[0018] Those skilled in the art should understand that the provision of the catalytic carbonization device downstream of the depolymerization device 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 may also include 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 provided downstream of the depolymerization device". Therefore, according to an embodiment of the present invention, the depolymerization device may be directly connected or not directly connected to the catalytic carbonization device.

[0019] According to an embodiment of the present invention, 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.

[0020] 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.

[0021] According to an embodiment of the present invention, 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.

[0022] According to an embodiment of the present invention, the solid-liquid mixed material comprises organic carbon.

[0023] According to an embodiment of the present invention, the unit A can be used to treat materials containing organic carbon, such as urban 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 urban garbage, domestic garbage, restaurant kitchen garbage, kitchen waste, municipal feces, sewage treatment sludge, water body sediment, garbage leachate, wood waste residue, crop straw, peat, lignite, bituminous coal, etc.

[0024] 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 peat, lignite, bituminous coal, etc., it can be directly catalytically carbonized.

[0025] According to an embodiment of the present invention, 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.

[0026] According to an embodiment of the present invention, 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.

[0027] According to an embodiment of the present invention, the hydrothermal carbonization system may further include a steam generating device to provide the depolymerization device with steam required for the depolymerization reaction.

[0028] According to an embodiment of the present invention, the steam generating device may also provide the catalytic carbonization device with steam required for the carbonization reaction.

[0029] According to an embodiment of the present invention, the depolymerization device may be provided with at least one air inlet so that the steam in the steam generating device enters the depolymerization device.

[0030] According to an embodiment of the present invention, 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.

[0031] 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.

[0032] According to an embodiment of the present invention, the depolymerization device may further be provided with at least one outlet for depolymerization gas phase material and at least one outlet for depolymerization non-gas phase material.

[0033] 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.

[0034] According to an embodiment of the present invention, the depolymerization gas phase material outlet of the depolymerization device is connected to the inlet of the depolymerization gas phase treatment device. The depolymerization gas phase treatment device may include a gas first phase cooling device and / or a first gas phase purification device, preferably including a first phase cooling device and a first gas phase purification device.

[0035] According to an embodiment of the present invention, 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.

[0036] According to an embodiment of the present invention, 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.

[0037] According to an embodiment of the present invention, the unit A further comprises a spiral flow controller to promote the reaction in the depolymerization device and / or the catalytic carbonization device.

[0038] According to an embodiment of the present invention, the depolymerization device and / or the catalytic carbonization device is preferably a horizontal tube reaction device.

[0039] According to an embodiment of the present invention, the catalytic carbonization device is provided with at least one air inlet so that the steam in the steam generating device enters the catalytic carbonization device.

[0040] According to an embodiment of the present invention, 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.

[0041] According to an embodiment of the present invention, 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.

[0042] According to an embodiment of the present invention, the catalytic carbonization device may also be provided with at least one carbonized gas phase material outlet and at least one carbonized solid-liquid-gas 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.

[0043] According to an embodiment of the present invention, 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.

[0044] According to an embodiment of the present invention, the carbonized product separation device is provided with at least one carbonized gas phase material outlet and at least one carbonized solid-liquid-gas 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.

[0045] According to an embodiment of the present invention, the condensate obtained by cooling the carbonized gas phase material can be mixed with the material provided by the feeding device, for example, it can be mixed with the material provided by the feeding device in a raw material mixer. Therefore, the carbonized gas phase processing device can be connected to the raw material mixer through a liquid phase delivery pipeline.

[0046] According to an embodiment of the present invention, the carbonization gas phase treatment device may be connected to the discharge device through a gas phase delivery pipeline, so that the gas obtained after being treated by the carbonization gas phase treatment device enters the discharge device for discharge.

[0047] According to an embodiment of the present invention, the carbonized solid-liquid-gas mixture material comprises a mixture of solid material, liquid material and gas material.

[0048] According to an embodiment of the present invention, a solid-liquid separation device, such as a centrifuge, is further provided downstream of the carbonized product separation device. Preferably, the outlet of the carbonized solid-liquid-gas 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.

[0049] According to an embodiment of the present invention, the solid-liquid separation device is provided with at least one carbonized solid phase material outlet to provide a carbonized solid phase product.

[0050] According to an embodiment of the present invention, the solid-liquid separation device is provided with at least one carbonized liquid phase material outlet to provide a carbonized liquid phase product.

[0051] According to an embodiment of the present invention, a heavy metal separation device is provided downstream of the solid-liquid separation device. Preferably, the heavy metal separation device can separate 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.

[0052] 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.

[0053] According to an embodiment of the present invention, the temperature of the material entering the catalytic carbonization device after passing through the buffer separation device is lower than the temperature of the material before entering the buffer separation device.

[0054] According to an embodiment of the present invention, the hydrothermal carbonization system is further provided with a heat recovery device to use the heat released by the system to preheat the material provided by the feeding device. For example, the preheating can be achieved by an 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.

[0055] 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 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 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.

[0056] According to an embodiment of the present invention, when the material needs to be cooled, circulating water can be selected for cooling. To this end, the cooling device of the present invention can also be provided with a pipeline for circulating cooling water.

[0057] According to an embodiment of the present invention, the temperature for depolymerization of the organic carbon-containing material in the depolymerization device may be about 230-240° C., and the depolymerization time may be about 5-30 min.

[0058] According to an embodiment of the present invention, 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.

[0059] According to an embodiment of the present invention, the unit A may also include one, two or more pre-treatment devices for pre-treating the organic carbon-containing material (or referred to as "pre-treatment") before depolymerization. For example, the pre-treatment includes but is not limited to pre-treating the organic carbon-containing material by crushing, pulping, depolymerizing, extracting, soaking, etc.

[0060] According to an embodiment of the present invention, the additive may be an additional additive required for any of the devices in the unit A 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.

[0061] According to an embodiment of the present invention, the solid acid catalyst may be the fly ash zeolite-based composite nano oxygen carrier described in Chinese patent application 202311217726.6.

[0062] According to an embodiment of the present invention, the fly ash is a tiny ash particle discharged during the combustion of fuel, optionally containing or not containing unburned carbonaceous particles, including unburned carbonaceous particles, also known as fly ash or smoke ash. In a preferred embodiment, the fly ash is boiler combustion fly ash, such as fly ash generated by unit B, more preferably all from fly ash generated by unit B.

[0063] According to an embodiment of the present invention, the oxygen carrier is prepared from fly ash. Preferably, the oxygen carrier is a chemical looping combustion oxygen carrier.

[0064] According to an embodiment of the present invention, 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 comprising 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.

[0065] 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.

[0066] According to an embodiment of the present invention, the solid acid catalyst or the oxygen carrier is referred to as a primary dispersion in the embodiment of the present invention because it has the above-mentioned dispersed structure.

[0067] According to an embodiment of the present invention, the oxygen carrier has a crystal structure of FAU zeolite.

[0068] According to an embodiment of the present invention, 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.

[0069] According to an embodiment of the present invention, when the metal oxide is ferric oxide, it may have a nanocrystalline particle structure of γ-Fe2O3, α-Fe2O3, or γ-Fe3O4.

[0070] According to an embodiment of the present invention, the metal of the metal oxide is derived from the metal contained in the fly ash itself, or from 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.

[0071] According to an embodiment of the present invention, the metal oxide may be nanoparticles. For example, the size of the nanoparticles is 0.1-100 nm, such as 1-50 nm, and exemplified by 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50 nm.

[0072] According to an embodiment of the present invention, the metal oxide nanoparticles are ferric oxide nanoparticles with a particle size of 3-5 nm.

[0073] According to an embodiment of the present invention, the particle shape of the metal oxide may be circular, ellipsoidal or other regular or irregular shapes.

[0074] According to an embodiment of the present invention, the oxygen carrier is a micro-nano material, that is, has a micro-nanoscale crystal structure.

[0075] 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%, 30 wt%.

[0076] According to an embodiment of the present invention, 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.

[0077] According to an embodiment of the present invention, the oxygen carrier is prepared from fly ash as raw material through a fusion polymerization (melt polymerization)-hydrothermal double-stage alkali conversion method.

[0078] According to an embodiment of the present invention, 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.

[0079] According to an embodiment of the present invention, 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).

[0080] According to an embodiment of the present invention, 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.

[0081] 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).

[0082] In one embodiment, the metal compound is the corresponding metal salt or oxide.

[0083] 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.

[0084] According to an embodiment of the present invention, 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.

[0085] According to an embodiment of the present invention, the solid acid catalyst may be a nanocomposite zeolite material described in Chinese patent application 202310381676.9.

[0086] According to an embodiment of the present invention, the nanoscale crystal structure of the nanocomposite zeolite material is a FAU / Zeolite structure, preferably a FAU / Zeolite Y-type structure.

[0087] According to an embodiment of the present invention, the nanocomposite zeolite material has micro-mesoporous cage void spaces.

[0088] According to an embodiment of the present invention, the nanocomposite zeolite material is aluminosilicate hydrate.

[0089] 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.

[0090] According to an embodiment of the present invention, the nanocomposite zeolite material is of a Fugarst zeolite type structure (FAU).

[0091] According to an embodiment of the present invention, the nanocomposite zeolite material has a three-level pore structure: the pore diameter of the first-level pore structure does not exceed 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.

[0092] According to an embodiment of the present invention, the sum of the specific surface areas of the nanocomposite zeolite materials is 150 to 1500 m 2 / g, for example 300~1200m 2 / g, such as 500~1000m 2 / g.

[0093] According to an embodiment of the present invention, the cation exchange capacity (CEC) of the nanocomposite zeolite material is 150-250 cmol (+) / kg.

[0094] According to an embodiment of the present invention, the pore volume of the nanocomposite zeolite material exceeds 50%, for example, exceeds 60%, such as 65-80%.

[0095] According to an embodiment of the present invention, the mass density of the nanocomposite zeolite material is 2.1-2.2 g / cc.

[0096] According to an embodiment of the present invention, the nanocomposite zeolite material has water holding capacity (water holding capacity 50 wt %).

[0097] According to an embodiment of the present invention, the nanocomposite zeolite material is insoluble in water at any pH. Alternatively, the nanocomposite zeolite material has acid and alkali resistance properties, that is, it is neither soluble in alkali (high pH) nor in acid (low pH).

[0098] According to an embodiment of the present invention, the fly ash includes but is not limited to one, two or more of the following sources: coal-fired power plants, waste incineration plants, boiler combustion sites, etc., such as 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.

[0099] According to an embodiment of the present invention, each device in the unit A 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 and then reacts.

[0100] 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.

[0101] According to an embodiment of the present invention, the additive is used as a catalyst to catalyze the hydrothermal carbonization reaction in the catalytic carbonization device. And preferably, after the hydrothermal carbonization reaction, the zeolite-based primary dispersion of the additive is further dispersed in water coke for a secondary time.

[0102] According to an embodiment of the present invention, 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.

[0103] According to an embodiment of the present invention, 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, such as 170°C on average; 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.

[0104] According to an embodiment of the present invention, the product of the unit A is a water coke slurry containing the additive (such as a solid acid catalyst).

[0105] According to an embodiment of the present invention, the product of unit A can be subjected to filter pressing, drying and / or pelletizing to prepare a catalytic combustion-supporting fuel product. Preferably, the particle size of the catalytic combustion-supporting fuel product can be adjusted to make it suitable for the requirements or standards of subsequent units.

[0106] According to an embodiment of the present invention, the unit A may further include a storage device for storing the obtained catalytic combustion-supporting fuel product.

[0107]

Unit B

[0108] According to an embodiment of the present invention, the unit B is used for catalytic hydrochar combustion (C-HCC for short).

[0109] According to an embodiment of the present invention, the catalytic water-carbon combustion unit B is located downstream of the unit A.

[0110] According to an embodiment of the present invention, in the unit B, the product of the unit A is burned (or incinerated) in the presence of a catalytic combustion-supporting fuel prepared by filter pressing, drying and / or granulation.

[0111] According to an embodiment of the present invention, the unit B includes a combustion device or an incineration device, which may be a municipal organic solid waste incineration boiler and / or a biomass incineration boiler known in the art.

[0112] According to an embodiment of the present invention, the combustion device includes a flue gas treatment module connected to the combustion furnace, including a waste heat furnace, a desulfurization device and / or a dust collector. In one embodiment, the flue gas treatment module includes a waste heat furnace, a desulfurization device and a dust collector connected in sequence, and the flue gas discharged from the combustion furnace is sequentially processed by waste heat recovery, desulfurization and dust removal and other cleaning links.

[0113] According to an embodiment of the present invention, the combustion device further comprises a circulation loop for clean flue gas to enter the furnace.

[0114] According to an embodiment of the present invention, the combustion device further comprises an air preheater.

[0115] In one embodiment, the combustion device includes a cleaned flue gas circuit, which is provided with two branches. The first branch passes through an air preheater to become a heat transfer medium for forming a CO2-enriched furnace and a nitrogen-free atmosphere, and the second branch produces a CO2-enriched gas, which is output as an industrial use of carbon sequestration or CO2 gas raw material.

[0116] According to an embodiment of the present invention, the combustion device further comprises a combustion furnace flue gas circuit, which is connected in parallel with a pipeline of a backup oxygen supply device for blowing into the furnace.

[0117]

Unit C

[0118] According to an embodiment of the present invention, the unit C is used to prepare the additive in the unit A, for example, the solid acid catalyst is prepared by fly ash alkali fusion hydrothermal zeolite (FA-HTZ).

[0119] According to an embodiment of the present invention, the unit C comprises a polymerization reactor, a grinding device, a dilution tank, an ultrasonic device and a hydrothermal activation device which are connected in sequence.

[0120] According to an embodiment of the present invention, the polymerization reactor is provided with a fly ash inlet and an alkaline agent inlet.

[0121] According to an embodiment of the present invention, the unit C 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.

[0122] According to an embodiment of the present invention, the additive is prepared by using fly ash as raw material through a fusion-hydrothermal dual-stage alkali conversion method.

[0123] According to an embodiment of the present invention, 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 a hydrothermal activation reaction to obtain the oxygen carrier.

[0124] According to an embodiment of the present invention, the alkaline condition may be provided by a strong base, for example, the strong base is potassium hydroxide and / or sodium hydroxide.

[0125] According to an embodiment of the present invention, the conditions for the smelting include: a temperature of 400-650° C. and a time of 2-8 h; for example, a temperature of 450-550° C. and a time of 4-6 h.

[0126] According to an embodiment of the present invention, the polymer is ground to 0.075 mm to 0.2 mm.

[0127] 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.

[0128] According to an embodiment of the present invention, the diluent used for dilution is water or a liquid medium recovered from a hydrothermal activation reaction.

[0129] According to an embodiment of the present invention, the dilution may or may not be performed with fly ash.

[0130] According to an embodiment of the present invention, the ultrasonic treatment time is 10-30 min, for example 15 min.

[0131] According to an embodiment of the present invention, 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.

[0132] 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.

[0133] According to an embodiment of the present invention, the process of the melting stage includes: mixing fly ash with alkali, heating and melting, grinding, and diluting to obtain a crystallization precursor solution.

[0134] Wherein, the base is selected from a strong base, such as sodium hydroxide.

[0135] 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.

[0136] According to an embodiment of the present invention, 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.

[0137] 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.

[0138] According to an 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.

[0139] 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.

[0140] According to an embodiment of the present invention, the dopant is added to the crystallization precursor solution, but when N=1 and N≥2, the preparation of the crystallization precursor solution is different:

[0141] 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;

[0142] 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.

[0143] 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.

[0144] According to an embodiment of the present invention, the temperature of the hydrothermal process is 90 to 170° C. and the time is 2 to 48 hours.

[0145] According to an embodiment of the present invention, the solid acid catalyst may be the fly ash zeolite-based composite nano oxygen carrier described in Chinese patent application 202311217726.6.

[0146] According to an embodiment of the present invention, the fly ash is a tiny ash particle discharged during the combustion of fuel, optionally containing or not containing unburned carbonaceous particles, including unburned carbonaceous particles, also known as fly ash or smoke ash. In a preferred embodiment, the fly ash is boiler combustion fly ash, such as fly ash generated by unit B, more preferably all from fly ash generated by unit B.

[0147] According to an embodiment of the present invention, the oxygen carrier is prepared from fly ash. Preferably, the oxygen carrier is a chemical looping combustion oxygen carrier.

[0148] According to an embodiment of the present invention, 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.

[0149] 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.

[0150] According to an embodiment of the present invention, the oxygen carrier has a crystal structure of FAU zeolite.

[0151] According to an embodiment of the present invention, 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.

[0152] According to an embodiment of the present invention, when the metal oxide is ferric oxide, it may have a nanocrystalline particle structure of γ-Fe2O3, α-Fe2O3, or γ-Fe3O4.

[0153] According to an embodiment of the present invention, the metal of the metal oxide is derived from the metal contained in the fly ash itself, or from 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.

[0154] Those skilled in the art should understand that when the chemical chaining combustion system is started, metal or metal oxide can be added to the fly ash in unit C as needed so that the solid acid catalyst has a sufficient amount of metal oxide. After the chemical chaining combustion 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 units A, B, C, and D of the combustion system of the present invention are each closed, and the connecting pipelines between A, B, C, and D are closed to reduce or avoid unnecessary consumption of metal elements.

[0155] According to an embodiment of the present invention, the metal oxide may be nanoparticles. For example, the size of the nanoparticles is 0.1-100 nm, such as 1-50 nm, and exemplified by 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50 nm.

[0156] According to an embodiment of the present invention, the metal oxide nanoparticles are ferric oxide nanoparticles with a particle size of 3-5 nm.

[0157] According to an embodiment of the present invention, the particle shape of the metal oxide may be circular, ellipsoidal or other regular or irregular shapes.

[0158] According to an embodiment of the present invention, the oxygen carrier is a micro-nano material, that is, has a micro-nanoscale crystal structure.

[0159] 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%, 30 wt%.

[0160] According to an embodiment of the present invention, 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.

[0161] According to an embodiment of the present invention, the oxygen carrier is prepared from fly ash as raw material through a fusion polymerization (melt polymerization)-hydrothermal double-stage alkali conversion method.

[0162] According to an embodiment of the present invention, 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.

[0163] According to an embodiment of the present invention, 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).

[0164] According to an embodiment of the present invention, 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.

[0165] 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).

[0166] In one embodiment, the metal compound is the corresponding metal salt or oxide.

[0167] 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.

[0168] 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.

[0169] According to an embodiment of the present invention, 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.

[0170] 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.

[0171] According to an embodiment of the present invention, the solid acid catalyst may be a nanocomposite zeolite material described in Chinese patent application 202310381676.9.

[0172] According to an embodiment of the present invention, the nanoscale crystal structure of the nanocomposite zeolite material is a FAU / Zeolite structure, preferably a FAU / Zeolite Y-type structure.

[0173] According to an embodiment of the present invention, the nanocomposite zeolite material has micro-mesoporous cage void spaces.

[0174] According to an embodiment of the present invention, the nanocomposite zeolite material is aluminosilicate hydrate.

[0175] 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.

[0176] According to an embodiment of the present invention, the nanocomposite zeolite material is of a Fugarst zeolite type structure (FAU).

[0177] According to an embodiment of the present invention, the nanocomposite zeolite material has a three-level pore structure: the pore diameter of the first-level pore structure does not exceed 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.

[0178] According to an embodiment of the present invention, the sum of the specific surface areas of the nanocomposite zeolite materials is 150 to 1500 m 2 / g, for example 300~1200m 2 / g, such as 500~1000m 2 / g.

[0179] According to an embodiment of the present invention, the cation exchange capacity (CEC) of the nanocomposite zeolite material is 150-250 cmol (+) / kg.

[0180] According to an embodiment of the present invention, the pore volume of the nanocomposite zeolite material exceeds 50%, for example, exceeds 60%, such as 65-80%.

[0181] According to an embodiment of the present invention, the mass density of the nanocomposite zeolite material is 2.1-2.2 g / cc.

[0182] According to an embodiment of the present invention, the nanocomposite zeolite material has water holding capacity (water holding capacity 50 wt %).

[0183] According to an embodiment of the present invention, the nanocomposite zeolite material is insoluble in water at any pH. Alternatively, the nanocomposite zeolite material has acid and alkali resistance properties, that is, it is neither soluble in alkali (high pH) nor in acid (low pH).

[0184] According to an embodiment of the present invention, the fly ash includes but is not limited to one, two or more of the following sources: coal-fired power plants, waste incineration plants, boiler combustion sites, etc., such as 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.

[0185] According to an embodiment of the present invention, the fly ash may be the fly ash mentioned above, preferably fly ash generated from combustion or incineration of unit B.

[0186] According to an embodiment of the present invention, after the hydrothermal activation reaction is completed, the product is filtered, washed and dried to obtain the additive (such as the oxygen carrier).

[0187]

Unit D

[0188] According to an embodiment of the present invention, the unit D is used to transport the additive produced by the unit C to the unit A so as to be mixed with the pre-treated organic carbon-containing material.

[0189] According to the embodiment of the present invention, there is no particular limitation on the specific device of the unit D, as long as it can transport the additive produced by the unit C to the unit A to mix with the pre-treated organic carbon-containing material.

[0190] The present invention also provides an integrated system, comprising the combustion system and a power generation system, wherein the H2O, CO2 and hot air flow generated by the combustion system are output to generate electricity through heat exchange.

[0191] According to an embodiment of the present invention, the power generation system is a power generation system known in the art.

[0192] The present invention also provides a method for generating electricity, comprising using the combustion system or integrated system to generate electricity, for example, using the combustion system to process materials containing organic carbon, and using a power generation system to generate electricity.

[0193] The present invention also provides a method for treating a material containing organic carbon, comprising using the combustion system to treat the material containing organic carbon.

[0194] The present invention also provides a use of a material containing organic carbon, which is used in the combustion system.

[0195] Beneficial Effects

[0196] The present invention is based on the following concept: the combustion residue of the boiler is mainly fly ash containing silicon oxide and aluminum oxide, which is rich in alkali metals and transition metals. A set of fly ash alkali melting hydrothermal zeolite process units are arranged in situ in the boiler combustion system, and heterogeneous metals such as K, Na, Al, Mg, Fe, Zn, Pb, Mn, and Cu are added according to the formula. The fly ash solid waste can be synthesized in situ with high activity solid acid catalytic zeolite materials through the arranged fly ash alkali melting hydrothermal zeolite process. After completing the first step of preparing the fly ash into a solid acid catalytic zeolite material in situ, it is necessary to add the material as a catalyst into the hydrothermal carbonization unit of the biomass fuel pretreatment of the boiler combustion system - as a catalyst to promote the hydrothermal carbonization yield. The hydrothermal carbonization (C-HTC) treatment under the action of the catalyst is the second step in which the solid acid catalyst reacts with the organic components of the biomass depolymerization. This step will produce water coke that supports a large number of secondary dispersed high-activity and high-density metal acid points. Under the action of the catalyst, the hydrothermal process synthesizes low-value biomass raw materials into high-calorific value water coke fuel carrying a large amount of heterogeneous metal catalytic combustion-supporting oxygen carriers. As a high-quality fuel carrying a large amount of heterogeneous metal catalytic combustion-supporting agents, water coke then enters the boiler combustion atmosphere and leads to the fuel gas molecules in the boiler atmosphere, producing catalytic combustion on the surface of highly active metal particles. The ashes after combustion react with air to re-form oxide-enriched fly ash. Therefore, the technical approach to in-situ resource utilization of fly ash designed by the present invention constructs a circulation loop of oxidation, zeolite, and reduction of combustion ash metals, forming an "oxidation, synthesis, and reduction" chemical chain circulation architecture of oxygen-carrying catalytic materials; and creates a chemical chain boiler combustion technology for an efficient biomass energy thermal power system. While the fly ash solid waste metals are recycled and utilized, the catalysis enhances the efficiency of the hydrothermal carbonization reaction of biomass; the catalysis improves the oxidation efficiency of water coke boiler combustion.

[0197] The present invention uses residual fly ash from the combustion of biomass thermal power boilers to synthesize zeolite-based solid acid catalytic materials in situ, and also serves as a bifunctional catalyst in situ to improve the efficiency of the "hydrothermal carbonization / hydrocarbon combustion" process in the novel biomass thermal power system.

[0198] In order to avoid the blockage of the reactor inlet and outlet caused by the addition of large doses of catalytic materials and to avoid the production capacity bottleneck of biomass carbon conversion, the C-HTC device described in the present invention has been upgraded, and the pump flow control for continuous processing of reactants has been changed to spiral propulsion flow control, and the carbonization reactor has been changed from a vertical type to a horizontal tube carbonization reaction device. The above-mentioned biomass undergoes catalytic reaction in the C-HTC spiral propulsion carbonization reaction horizontal tube device, and the fly ash zeolite-based heterogeneous metal solid acid catalytic material output produced also establishes a "feedback" loop for the output of C-HTC catalytic carbonization materials for biomass raw materials through a secondary dispersion process, which can further promote the efficiency and yield of biomass conversion into solid water coke.

[0199] The functional layout of the in-situ production of fly ash zeolite-based catalytic materials in the present invention has pioneered a nanotechnology approach to thermochemical catalytic efficiency enhancement in the process of biomass thermoelectric conversion, achieved the in-situ regeneration of solid waste into catalytic materials and the in-situ use of the catalytic materials, and constructed an "efficient chemical chain loop of oxidation / reduction" for the in-situ low-cost production and in-situ high-value application of solid metal oxide catalysts; in addition, the present invention designs the fly ash zeolite-based solid acid catalyst with a dual-phase catalytic function as a single material, which simplifies the complexity of the industrial process and reduces the overall cost of the system.

[0200] The present invention uses the combustion residue (fly ash) of the biomass thermal power boiler to synthesize zeolite-based catalytic materials in situ of the system. The material is used as a dual-function catalyst to improve the efficiency of the "hydrothermal carbonization / hydrocarbon combustion" process in the biomass thermal power system. Under the system layout framework of in-situ production of zeolite-based catalytic materials, the in-situ recycling of fly ash solid waste and the sustainable catalytic efficiency enhancement of thermochemistry in the biomass thermal power conversion process are realized. The fly ash zeolite-based catalytic material will be used in two thermochemical processes of the system in sequence: (1) catalytically promoting the process efficiency of biomass conversion to hydrochar (C-HTC) reaction; (2) catalytically promoting the boiler clean combustion efficiency of the hydrocarbon combustion-assisted C-HCC reaction; at the same time, the present invention uses a single recycled material for dual-phase catalysis, which also simplifies the complexity of the industrial process and reduces the cost of the system. The present invention can only make minor modifications on the basis of retaining the core equipment of the mature carbonaceous fuel boiler power generation system, that is, it can upgrade the traditional carbonaceous boiler power generation system to an advanced chemical chain combustion power generation system, overcoming the technical difficulty that the existing boiler system cannot be upgraded because the CLC system based on the gas-solid reactor process prototype of the double interconnected fluidized bed is different from the process of the current boiler equipment of most coal-fired power generation units in the world. This provides an economically feasible technical approach for upgrading and transforming the traditional biomass thermal power system deployed on a large scale in China into an advanced chemical chain combustion power generation system. BRIEF DESCRIPTION OF THE DRAWINGS

[0201] Figure 1 This is a schematic diagram of the biomass thermal power system of the present invention;

[0202] The meanings of the various reference numerals are as follows: A1-urban garbage; A2-receiving silo; A3-pulping machine; A4-slag extractor; A5-pressing machine; A6-slag box; A7-sand and impurity removal; A8-heating and oil extraction; A9-temporary storage of hot liquid; A10-mixing and homogenization; A11-transportation of sand, gravel and light materials; A12-crude oil; A13-washing water; A14-low-level water tank.

[0203] B1-food waste; B2-receiving silo; B3-pulping machine; B4-slag lifter; B5-pressing machine; B6-slag box; B7-sand and impurity removal; B8-heating and oil extraction; B9-temporary storage of hot liquid; B10-mixing and homogenization; B11-transportation of sand, gravel and light materials; B12-crude oil; B13-flushing water; B14-low-level water tank; B15-food waste; B16-receiving silo; B17-pulping machine; B18-slag lifter; B19-pressing machine; B20-slag box; B21-transportation of impurities; B22-flushing water; B23-sand and impurity removal; B24-grease trap; B25-solid-liquid separation; B26-municipal feces; B27-integrated impurity removal equipment; B28-water tank; B29-low-level water tank; B30-flushing water; B31-transportation of impurities.

[0204] C1-mixing tank; C2-distribution screw; C3-pin drum meter; C4-heating screw; C5-feeding screw; C6-T-tube; C7-cooking tube; C8-mud separation; C9-automatic sedimentation centrifuge; C10-granulation molding machine; C11-water coke; C12-dehydration storage tank; C13-heavy metal removal; C14-liquid product tanker; C15-metering screw; C16-high-pressure screw feeder; C17-feeder piston; C18-depolymerization reactor; C19-buffer separation; C2 0-mud; C21-gas; C22-exhaust cooler; C23-exhaust separator; C24-exhaust adsorber; C25-discharge; C26-spray cooling tower; C27-spray cooler; C28-external circulating water; C29-external circulating water; C30-cellulose, hemicellulose slurry; C31-backflush cyclone; C32-steam; C33-secondary dispersion loop; C34-external circulating water; C35-external circulating water; C36-solids; C37-barrelling; C38-external water.

[0205] D1-incinerator; D2-waste heat boiler; D3-desulfurization; D4-dust collector; D5-air preheater; D6-deaerator; D7-condenser; D8-steam turbine generator; D9-boiler; D10-slag remover; D11-slag pit; D12-slag crane; D13-fly ash; D14-OXY-FUEL.

[0206] E1-fly ash storage tank with vibrator; E2-screw conveyor for transporting fly ash; E3-NaOH storage tank with vibrator; E4-screw conveyor for transporting NaOH; E5-weighing tank with vibrator and three strain gauge weight sensors; E6-calciner feeder; E7-calciner; E8-grinding; E9-dilution in water; E10-ultrasonic treatment; E11-mixer; E12-heater; E13-hydrothermal activation; E14-filter press; E15-external water; E16-washing; E17-fly ash zeolite-based nanocomposite; E18-adding one-third of the total amount of raw ash; E19-fly ash storage tank with vibrator; E20-screw conveyor for transporting fly ash ; E21 - screw conveyor for transporting fly ash; E22 - storage tank for fly ash and other raw materials with vibrator; E23 - screw conveyor for transporting fly ash; E24 - storage tank for NaOH with vibrator; E25 - screw conveyor for transporting NaOH; E26 - weighing tank with vibrator and three strain gauge weight sensors; E27 - dilution in water; E28 - ultrasonic treatment; E29 - agitator; E30 - heater; E31 - hydrothermal activation; E32 - filter press; E33 - external water; E34 - washing; E35 - fly ash zeolite-based nanocomposite material; E36 - aqueous NaOH solution; E37 - reuse of alkaline water; E38 - external water; E39 - reuse of alkaline water.

[0207] Figure 2 It is a pre-treatment device for hydrothermal carbonization biomass slurry feed.

[0208] Figure 3 It is a biomass raw material pretreatment (C-HTC) device.

[0209] Figure 4 The invention relates to a device for in-situ synthesis of zeolite-based acid catalytic materials (FA-HTZ) from fly ash.

[0210] Figure 5 This is the schematic diagram of traditional chemical loop combustion.

[0211] Figure 6 This is a schematic diagram of the chemical loop combustion principle of the present invention.

[0212] Figure 7 This is a schematic diagram of the system for hydrothermal carbonization / hydrocarbon combustion / fly ash zeolite C-HTC / C-HCC / FA-HTC catalytic enhanced biomass thermal conversion. DETAILED DESCRIPTION

[0213] The following will further explain in detail the technical solution of the biomass thermal power energy system with a new thermochemical catalytic efficiency enhancement architecture in combination with a specific implementation plan.

[0214] It should be understood that the following embodiments are only exemplary illustrations and explanations of the present invention, and should not be interpreted as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are included in the scope of protection intended by the present invention.

[0215] Unless otherwise specified, the raw materials and reagents used in the following embodiments are commercially available or can be prepared by known methods.

[0216] Example 1

[0217] This embodiment provides a combustion system, including:

[0218] Unit A for catalytic hydrothermal carbonization;

[0219] A unit B located downstream of the unit A and used for combustion;

[0220] a unit C located downstream of the unit B and used to prepare the additive in the unit A; and

[0221] The additive produced by unit C is conveyed to the transfer unit D of unit A.

[0222] in:

[0223]

Unit A

[0224] The unit A is used for catalytic hydrothermal carbonization (C-HTC for short).

[0225] The unit A comprises a catalytic carbonization device, or comprises a depolymerization device and a catalytic carbonization device disposed downstream of the depolymerization device.

[0226] 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.

[0227] Disposing the catalytic carbonization device downstream of the depolymerization device 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 an embodiment of the present invention, the depolymerization device may be directly connected to the catalytic carbonization device or not directly connected.

[0228] 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.

[0229] 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.

[0230] The solid-liquid mixture contains organic carbon. For example, the solid-liquid mixture is selected from one or a mixture of two or more materials containing organic carbon, such as domestic garbage, kitchen garbage, sewage treatment sludge, water body sediment, garbage leachate, wood waste, crop straw, etc.

[0231] 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.

[0232] 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.

[0233] The hydrothermal carbonization system may further include a steam generating device to provide the depolymerization device with steam required for the depolymerization reaction.

[0234] The steam generating device can also provide the catalytic carbonization device with steam required for the carbonization reaction.

[0235] 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.

[0236] 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.

[0237] 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.

[0238] 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.

[0239] 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.

[0240] 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.

[0241] 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.

[0242] 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.

[0243] The unit A further comprises a spiral flow controller to promote the reaction in the depolymerization device and / or the catalytic carbonization device. The catalytic carbonization device is a horizontal tube reaction device.

[0244] 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.

[0245] 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.

[0246] 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.

[0247] 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.

[0248] The carbonized solid-liquid-gas mixture material outlet of the catalytic carbonization device is connected to the inlet of the carbonization product separation device.

[0249] 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.

[0250] 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.

[0251] 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.

[0252] The carbonized solid-liquid-gas mixture material comprises a mixture of solid material, liquid material and gas material.

[0253] 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.

[0254] The solid-liquid separation device is provided with at least one carbonized solid phase material outlet to provide a carbonized solid phase product.

[0255] The solid-liquid separation device is provided with at least one carbonized liquid phase material outlet to provide a carbonized liquid phase product.

[0256] 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.

[0257] 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.

[0258] 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.

[0259] 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.

[0260] 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 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.

[0261] When the material needs to be cooled, circulating water can be selected for cooling. For this reason, the cooling device of the present invention can also be provided with a pipeline for circulating cooling water.

[0262] The unit A can be used to treat materials containing organic carbon, such as urban 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 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.

[0263] 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.

[0264] 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.

[0265] The unit A 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.

[0266] The additive is a fly ash zeolite-based composite nano oxygen carrier recorded in Chinese patent application 202311217726.6.

[0267] Each device in the unit A 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 and then reacts.

[0268] The additive reacts after being mixed with the organic carbon-containing material, so that the water coke product produced by the organic carbon-containing material through the C-HTC process becomes the carbon-based material support for the secondary dispersion of the zeolite-based loaded metal material, and the metal loaded in the zeolite structure becomes the primary dispersed nanoparticles in the water coke.

[0269] 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.

[0270] 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 catalytic carbonization device can be reduced to an average of 150 to 180°C, such as 170°C; and / or, the reaction time can be reduced to 30 to 120 min, for example, 20 to 60 min.

[0271] The product of the unit A is a water coke slurry containing the additive (eg, solid acid catalyst).

[0272] The product of the unit A can be passed through a filter press, drying and / or pelletizing device to prepare a catalytic combustion-supporting fuel product. Preferably, the particle size of the catalytic combustion-supporting fuel product can be adjusted to make it suitable for the requirements or standards of subsequent units.

[0273] The unit A may also include a storage device for storing the obtained catalytic combustion-supported fuel product.

[0274]

Unit B

[0275] The unit B is used for catalytic hydrochar combustion (C-HCC for short).

[0276] The catalytic water-carbon combustion unit B is located downstream of the unit A.

[0277] In the unit B, the product of the unit A is burned (or incinerated) in the presence of a catalytic combustion-supporting fuel prepared by filtering, drying and / or granulating the product of the unit A.

[0278] The unit B includes a combustion device or an incineration device, which may be a municipal organic solid waste incineration boiler and / or a biomass incineration boiler known in the art.

[0279] The combustion device includes a flue gas treatment module connected to the combustion furnace, including a waste heat furnace, a desulfurization device and / or a dust collector. In one embodiment, the flue gas treatment module includes a waste heat furnace, a desulfurization device and a dust collector connected in sequence, and the flue gas discharged from the combustion furnace is sequentially processed by waste heat recovery, desulfurization and dust removal and other cleaning links.

[0280] The combustion device also includes a circulation loop for clean flue gas to enter the furnace.

[0281] The combustion device also includes an air preheater.

[0282] In one embodiment, the combustion device includes a cleaned flue gas circuit, which is provided with two branches. The first branch passes through an air preheater to become a heat transfer medium for forming a CO2-enriched furnace and a nitrogen-free atmosphere, and the second branch produces a CO2-enriched gas, which is output as an industrial use of carbon sequestration or CO2 gas raw material.

[0283] The combustion device also includes a combustion furnace flue gas loop, which is connected in parallel with the pipeline of the backup oxygen supply device for injection into the furnace.

[0284]

Unit C

[0285] The unit C is used to prepare the additive in the unit A, for example, the solid acid catalyst is prepared by fly ash alkali melting hydrothermal zeolite (FA-HTZ).

[0286] The unit C comprises a polymerization reactor, a grinding device, a dilution tank, an ultrasonic device and a hydrothermal activation device which are connected in sequence.

[0287] The polymerization reactor is provided with a fly ash inlet and an alkaline reagent inlet.

[0288] The unit C also includes 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.

[0289] The additive is prepared by using fly ash as raw material through a fusion-hydrothermal double-stage alkali conversion method.

[0290] 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.

[0291] The alkaline condition can be provided by a strong base, for example, the strong base is potassium hydroxide and / or sodium hydroxide.

[0292] 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.

[0293] The polymer was ground to 0.075 mm to 0.2 mm.

[0294] The concentration of the solid matter in the diluted mixture is 1-5 mol / L, for example 2.5 mol / L.

[0295] The diluent used for dilution is water or the liquid medium recovered from the hydrothermal activation reaction.

[0296] The dilution may or may not be performed with the addition of fly ash.

[0297] The ultrasonic treatment time is 10-30 min, for example 15 min.

[0298] 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.

[0299] 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.

[0300] The process of the melting stage includes: mixing fly ash with alkali, heating and melting, grinding, and diluting to obtain a crystallization precursor solution.

[0301] Wherein, the base is selected from a strong base, such as sodium hydroxide.

[0302] 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.

[0303] 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.

[0304] 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.

[0305] 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.

[0306] 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.

[0307] 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:

[0308] 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;

[0309] 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.

[0310] 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.

[0311] The temperature of the hydrothermal process is 90-170°C and the time is 2-48 hours.

[0312] According to an embodiment of the present invention, the solid acid catalyst may be the fly ash zeolite-based composite nano oxygen carrier described in Chinese patent application 202311217726.6.

[0313] According to an embodiment of the present invention, the fly ash is a tiny ash particle discharged during the combustion of fuel, optionally containing or not containing unburned carbonaceous particles, including unburned carbonaceous particles, also known as fly ash or smoke ash. In a preferred embodiment, the fly ash is boiler combustion fly ash, such as fly ash generated by unit B, more preferably all from fly ash generated by unit B.

[0314] According to an embodiment of the present invention, the oxygen carrier is prepared from fly ash. Preferably, the oxygen carrier is a chemical looping combustion oxygen carrier.

[0315] According to an embodiment of the present invention, 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.

[0316] 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.

[0317] According to an embodiment of the present invention, the oxygen carrier has a crystal structure of FAU zeolite.

[0318] According to an embodiment of the present invention, 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.

[0319] According to an embodiment of the present invention, when the metal oxide is ferric oxide, it may have a nanocrystalline particle structure of γ-Fe2O3, α-Fe2O3, or γ-Fe3O4.

[0320] According to an embodiment of the present invention, the metal of the metal oxide is derived from the metal contained in the fly ash itself, or from 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.

[0321] Those skilled in the art should understand that when the chemical chaining combustion system is started, metal or metal oxide can be added to the fly ash in unit C as needed so that the solid acid catalyst has a sufficient amount of metal oxide. After the chemical chaining combustion 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 units A, B, C, and D of the combustion system of the present invention are each closed, and the connecting pipelines between A, B, C, and D are closed to reduce or avoid unnecessary consumption of metal elements.

[0322] According to an embodiment of the present invention, the metal oxide may be nanoparticles. For example, the size of the nanoparticles is 0.1-100 nm, such as 1-50 nm, and exemplified by 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50 nm.

[0323] According to an embodiment of the present invention, the metal oxide nanoparticles are ferric oxide nanoparticles with a particle size of 3-5 nm.

[0324] According to an embodiment of the present invention, the particle shape of the metal oxide may be circular, ellipsoidal or other regular or irregular shapes.

[0325] According to an embodiment of the present invention, the oxygen carrier is a micro-nano material, that is, has a micro-nanoscale crystal structure.

[0326] 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%, 30 wt%.

[0327] According to an embodiment of the present invention, 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.

[0328] According to an embodiment of the present invention, the oxygen carrier is prepared from fly ash as raw material through a fusion polymerization (melt polymerization)-hydrothermal double-stage alkali conversion method.

[0329] According to an embodiment of the present invention, 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.

[0330] According to an embodiment of the present invention, 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).

[0331] According to an embodiment of the present invention, 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.

[0332] 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).

[0333] In one embodiment, the metal compound is the corresponding metal salt or oxide.

[0334] 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.

[0335] According to an embodiment of the present invention, 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.

[0336] 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.

[0337] According to an embodiment of the present invention, the solid acid catalyst may be a nanocomposite zeolite material described in Chinese patent application 202310381676.9.

[0338] According to an embodiment of the present invention, the nanoscale crystal structure of the nanocomposite zeolite material is a FAU / Zeolite structure, preferably a FAU / Zeolite Y-type structure.

[0339] According to an embodiment of the present invention, the nanocomposite zeolite material has micro-mesoporous cage void spaces.

[0340] According to an embodiment of the present invention, the nanocomposite zeolite material is aluminosilicate hydrate.

[0341] 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.

[0342] According to an embodiment of the present invention, the nanocomposite zeolite material is of a Fugarst zeolite type structure (FAU).

[0343] According to an embodiment of the present invention, the nanocomposite zeolite material has a three-level pore structure: the pore diameter of the first-level pore structure does not exceed 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.

[0344] According to an embodiment of the present invention, the sum of the specific surface areas of the nanocomposite zeolite materials is 150 to 1500 m 2 / g, for example 300~1200m 2 / g, such as 500~1000m 2 / g.

[0345] According to an embodiment of the present invention, the cation exchange capacity (CEC) of the nanocomposite zeolite material is 150-250 cmol (+) / kg.

[0346] According to an embodiment of the present invention, the pore volume of the nanocomposite zeolite material exceeds 50%, for example, exceeds 60%, such as 65-80%.

[0347] According to an embodiment of the present invention, the mass density of the nanocomposite zeolite material is 2.1-2.2 g / cc.

[0348] According to an embodiment of the present invention, the nanocomposite zeolite material has water holding capacity (water holding capacity 50 wt %).

[0349] According to an embodiment of the present invention, the nanocomposite zeolite material is insoluble in water at any pH. Alternatively, the nanocomposite zeolite material has acid and alkali resistance properties, that is, it is neither soluble in alkali (high pH) nor in acid (low pH).

[0350] According to an embodiment of the present invention, the fly ash includes but is not limited to one, two or more of the following sources: coal-fired power plants, waste incineration plants, boiler combustion sites, etc., such as 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.

[0351] The fly ash comes from the fly ash generated by the combustion or incineration of unit B.

[0352] After the hydrothermal activation reaction is completed, the product is filtered, washed and dried to obtain the additive.

[0353]

Unit D

[0354] The unit D is used to transport the additive produced by the unit C to the unit A so as to be mixed with the organic carbon-containing material after pre-treatment.

[0355] There is no particular limitation on the specific device of the unit D, as long as it can transport the additive produced by the unit C to the unit A to mix with the pre-treated organic carbon-containing material.

[0356] Example 2

[0357] This embodiment provides another combustion system, which is different from Embodiment 1 only in that the additive is selected from the nanocomposite zeolite material described in Chinese Patent Application No. 202310381676.9.

[0358] Example 3

[0359] This embodiment provides an integrated system, including the combustion system of embodiment 1 or 2, and a power generation system, wherein the H2O, CO2, and hot air flow generated by the combustion system are output to generate electricity through heat exchange. The power generation system is a power generation system known in the art.

[0360] Example 4

[0361] Through Unit C (see Figure 4The fly ash in-situ synthesis of zeolite-based solid acid catalytic materials (FA-HTZ) device is used to prepare the zeolite-based solid acid catalyst by alkali fusion hydrothermal zeolitization (FA-HTZ) using the fly ash produced by unit B. The preparation method 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 zeolite-based solid acid catalyst.

[0362] Alkali melting conditions: Fly ash and sodium hydroxide are added to the polymerization reactor through the fly ash inlet and the alkaline reagent inlet respectively in a mass ratio of 1:1, and heated and melted after being fully mixed. The melting temperature is 600°C and the time is 2h. The material enters the grinding device, grinds the polymer to a particle size of <0.2mm, and then enters the dilution tank, and dilutes it with water at a solid concentration of 0.10g / mL. After ultrasonic treatment for 15min, ageing is carried out for 12h. After aging, it enters the hydrothermal activation device. At the same time, nano-cerium oxide with a particle size of less than 10nm is added for doping at a mass ratio of 1:5 between the dopant and the crystallization precursor solution, and the hydrothermal temperature is 120°C for 6h. After the hydrothermal activation reaction is completed, the product is filtered, washed, and dried to obtain a doped zeolite-based solid acid catalyst, and the nano-cerium oxide is evenly distributed in the zeolite carrier.

[0363] The test results of the doped zeolite-based solid acid catalyst (nanocomposite zeolite material) prepared in this example are shown in Table 1 below:

[0364] Table 1

[0365] Test items unit Test results Average pore size nm 8.1599 BET surface area <![CDATA[m 2 / g]]> 168.4831 Average nanoparticle size nm 43.3266 CEC cmol(+) / Kg 172.5

[0366] The above results show that the present invention uses the residual fly ash from the combustion of the unit B biomass thermal power boiler as raw material, successfully synthesizes zeolite-based solid acid catalytic materials in situ, realizes the in-situ regeneration of solid waste into catalytic materials and the value-added cycle of using the catalytic materials in situ, and constructs an "efficient chemical chain loop of oxidation / reduction" for in-situ low-cost production and in-situ high-value application of solid metal oxide catalysts. Under the system layout framework of in-situ production of zeolite-based catalytic materials, the in-situ recycling of fly ash solid waste is realized, and the sustainable catalytic efficiency enhancement of thermochemistry in the process of biomass thermal power conversion is realized.

[0367] Example 5

[0368] Catalytic hydrothermal carbonization (C-HTC) is carried out through unit A to prepare a catalytic combustion-supporting fuel product. The unit A includes a depolymerization device and a catalytic carbonization device arranged downstream of the depolymerization device. The material containing organic carbon and the solid acid catalyst produced in Example 4 are added in a weight ratio of 5:1, and after sufficient mixing, they enter the depolymerization device for reaction. The depolymerization reaction temperature is 240°C and the depolymerization time is 15min. After the reaction is completed, it enters the catalytic carbonization device, the reaction temperature is 170°C, and the reaction time is 30min. The product of unit A is a water coke slurry containing a solid acid catalyst, which is filtered through a filter press, drying and / or a granulation device to prepare a catalytic combustion-supporting fuel product. The catalytic combustion-supporting product can be used in unit B for catalytic water-carbon combustion.

[0369] The above results show that the present invention uses the residual fly ash from the combustion of the unit B biomass thermal power boiler as raw material, successfully synthesizes the zeolite-based solid acid catalytic material in situ, and uses the material as a bifunctional catalyst to improve the efficiency of the "hydrothermal carbonization / hydrocarbon combustion" process in the biomass thermal power system. Under the system layout framework of in-situ production of zeolite-based catalytic materials, the in-situ recycling of fly ash solid waste and the sustainable catalytic efficiency enhancement of thermochemistry in the biomass thermal power conversion process are realized. At the same time, the present invention uses a single regenerated material for dual-phase catalysis, which also simplifies the complexity of the industrial process and reduces the cost of the system. On the basis of retaining the core equipment of the mature carbonaceous fuel boiler power generation system, the present invention makes a minor modification, thereby upgrading the traditional carbonaceous boiler power generation system to an advanced chemical chain combustion power generation system, overcoming the technical difficulty that the CLC system based on the gas-solid reactor process prototype of the dual interconnected fluidized bed is different from the process of the current boiler equipment of most coal-fired power generation units in the world, making it impossible to upgrade the existing boiler system. Therefore, it provides an economically feasible technical approach for upgrading and transforming the traditional biomass thermal power system deployed on a large scale in China into an advanced chemical chain combustion power generation system.

[0370] The above examples are used to illustrate the specific implementation of the present invention. However, the protection scope of the present invention is not limited to the above exemplary implementation. Any modification, equivalent substitution, 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 combustion system, comprising: Unit A for catalytic hydrothermal carbonization; A unit B located downstream of the unit A and used for combustion; A unit C located downstream of the unit B and used to prepare the additive in the unit A; and The additive produced by unit C is conveyed to the transfer unit D of unit A.

2. The combustion system of claim 1, wherein: The unit A comprises a catalytic carbonization device, or comprises a depolymerization device and a catalytic carbonization device disposed downstream of the depolymerization device; The unit A also includes a spiral flow controller to promote the reaction in the depolymerization device and / or the catalytic carbonization device; The depolymerization device and / or catalytic carbonization device is preferably a horizontal tube reaction device.

3. The combustion system according to claim 1 or 2, wherein: The additive is an acidic catalyst, preferably a solid acidic catalyst or an oxygen carrier, such as the fly ash zeolite-based composite nano oxygen carrier described in Chinese patent application 202311217726.6 or the nanocomposite zeolite material described in Chinese patent application 202310381676.9; Preferably, the solid acid catalyst or oxygen carrier comprises a metal oxide and a carrier; preferably, the metal oxide is dispersed in the carrier.

4. The combustion system according to any one of claims 1 to 3, wherein: 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.

5. The combustion system of claim 4, wherein: The reaction temperature of the depolymerization device and / or the catalytic carbonization device is 150-180°C; and / or The reaction time of the depolymerization device and / or the catalytic carbonization device is 30 to 120 minutes, such as 20 to 60 minutes.

6. The combustion system according to any one of claims 1 to 5, wherein: The product of the unit A is passed through filter pressing, drying and / or granulation equipment to prepare a catalytic combustion-supporting fuel product.

7. The combustion system according to any one of claims 1 to 6, wherein: In the unit B, the product of the unit A is burned (or incinerated) in the presence of a catalytic combustion-supporting fuel prepared by filtering, drying and / or granulating the product of the unit A.

8. The combustion system according to any one of claims 1 to 7, wherein: The unit C is used to prepare the additive in the unit A, for example, the solid acid catalyst is prepared by fly ash alkali melting hydrothermal zeolite (FA-HTZ); The fly ash preferably comes from fly ash generated by combustion or incineration of unit B.

9. An integrated system, comprising a combustion system and a power generation system as claimed in any one of claims 1 to 8, wherein the H2O, CO2 and hot air flow generated by the combustion system are output to generate electricity through heat exchange.

10. A method for generating electricity, comprising generating electricity using a combustion system or an integrated system as described in any one of claims 1 to 8, for example, using the combustion system to process materials containing organic carbon, and using a power generation system to generate electricity.

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