Integrated system

Abstract

The utility model provides an integrated system which comprises a combustion system and a power generation system. The combustion system comprises: a unit A for catalytic hydrothermal carbonization; a unit B located downstream of the unit A and used for combustion; the unit C is positioned at the downstream of the unit B and is used for preparing the additive in the unit A; and a transport unit D for transporting the additive produced by the unit C to the unit A. According to the functional layout of in-situ production of the fly ash zeolite-based catalytic material, a nanotechnology approach for thermochemical catalytic synergism in a biomass thermoelectric conversion process is created, and value-added circulation of regenerating solid waste into the catalytic material in situ and using the catalytic material in situ is realized; 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 is a divisional application of the utility model patent application with the application date of March 4, 2024, application number 202420411258.X, and invention name “Chemical chaining combustion system of fly ash solid waste oxygen-carrying medium”. Technical Field

[0002] This utility model relates to a chemical looping combustion system for fly ash solid waste oxygen-carrying media. Specifically, it includes a technical approach for in-situ resource utilization of fly ash solid waste, as well as an implementation plan for applying this technical approach to the improvement and upgrade of traditional boiler combustion systems for biomass thermal power conversion. By applying this technical approach to the transformation of traditional boiler combustion systems, existing equipment in the traditional boiler combustion system can be maintained without changing them, but rather the traditional boiler combustion system can be directly upgraded to an advanced, high-efficiency chemical looping boiler combustion system. This utility model belongs to the field of fly ash solid waste resource utilization and novel chemical looping boiler combustion technology for biomass energy. Background Art

[0003] Biomass, Earth's "renewable carbon," originates from photosynthesis during plant growth. Plant cell walls (also known as "lignocellulose") are the most abundant biomass resource on Earth, with over 170 billion tons produced annually. Consequently, traditional boiler combustion technology for biomass thermal power conversion has long been the mainstream technology for biomass renewable energy in my country.

[0004] Biomass contains a large amount of water. When heated to 100°C, the boiling point of water at normal atmospheric pressure, the water begins to evaporate, consuming a large amount of heat energy. This is particularly true in boiler combustion systems that use biomass for thermoelectric conversion, where the biomass directly enters the boiler's combustion atmosphere for thermochemical reactions, consuming more than two-thirds of its own biomass energy and a large amount of water.

[0005] Furthermore, boiler combustion produces a large amount of fly ash, a complex of coal ash, mixed coal ash, dust, and other substances such as sulfates and nitrates produced during the combustion process. Fly ash is typically finely particulate, often suspended in the flue gas, and can be airborne into the surrounding environment. Because it contains a variety of hazardous substances, such as heavy metals, dioxins, and polycyclic aromatic hydrocarbons, fly ash poses a threat to both the environment and human health. A report analyzing the physical and chemical properties of fly ash generated by domestic waste incineration plants showed that the mass fraction of fly ash from grate furnaces using pure waste incineration is higher than that from fluidized bed incineration using mixed coal. Furthermore, the concentration of heavy metals in fly ash increases with decreasing fly ash particle size. The basic elements 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, and Cr.

[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. Utility Model Content

[0007] In order to improve the technical problems existing in the traditional biomass thermal power boiler system, the utility model provides a combustion system, including:

[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 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 the embodiment of the present invention, each unit of the combustion system can 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 includes a catalytic carbonization device, or includes a depolymerization device and a catalytic carbonization device disposed downstream of the depolymerization device.

[0017] According to the embodiment of the present invention, the catalytic carbonization device is arranged downstream of the depolymerization device so that the material is processed by the depolymerization device and then by the catalytic carbonization 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 as described herein may include not only a method of directly subjecting the material output from the depolymerization device to treatment by the catalytic carbonization device, but also a method of directly feeding 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 the embodiment of the present invention, the depolymerization device and the catalytic carbonization device may be directly connected or not directly connected.

[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 and the catalytic carbonization device are not directly connected, the material output from the depolymerization device may be processed first by the buffer separation device or other device, and then 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 to the depolymerization device. For example, the feeding device is a feeding device for a solid-liquid mixture material.

[0022] According to an embodiment of the present invention, the solid-liquid mixture material contains 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 municipal waste (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 municipal waste, domestic waste, restaurant waste, kitchen waste, municipal feces, sewage treatment sludge, water body sediment, landfill leachate, wood waste residue, crop straw, peat, lignite, bituminous coal, etc.

[0024] For example, when the organic carbon-containing material is selected from domestic waste, restaurant waste, kitchen waste, municipal feces, sewage treatment sludge, water body sediment, landfill leachate, wood waste residue, crop straw, etc., it can be first depolymerized and then catalytically carbonized. Alternatively, when the organic carbon-containing material is selected from peat, lignite, bituminous coal, etc., it can be directly catalytically carbonized.

[0025] According to an embodiment of the present invention, the deagglomeration device may be provided with at least one feed port, so that the material provided by the feed device enters the deagglomeration device.

[0026] According to an embodiment of the present invention, the material in the feeding device can directly enter the depolymerization device. Alternatively, a raw material mixer, a preheating mixer, and / or a mixing liquid storage tank can be provided between the feeding device and the depolymerization device, so that the material in the feeding device passes through the raw material mixer, the preheating mixer, and / or the mixing 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 can 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 further 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 additives may also enter the depolymerization device through the feed port of the solid-liquid mixture, as long as they 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 depolymerized gaseous materials and at least one outlet for depolymerized non-gaseous materials.

[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 and liquid materials that are processed by a depolymerization device and need to be further processed in a buffer separation device and / or a catalytic carbonization 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 first gas phase cooling device and / or a first gas phase purification device, preferably including a first gas phase cooling device and a first gas phase purification device.

[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 an exhaust device, so that the gas obtained after being treated by the depolymerization gas phase treatment device enters the exhaust device for exhaustion.

[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 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 the gaseous phase material from the non-gaseous phase material in the material 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 outlet for carbonized gaseous material and at least one outlet for carbonized solid-liquid-gas mixture material. Preferably, the outlet for carbonized gaseous 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 gaseous material.

[0043] According to the embodiment of the present utility model, the outlet of the carbonized solid-liquid-gas mixture material of the catalytic carbonization device is connected to the inlet of the carbonization product separation device.

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

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

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

[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 to separate the carbonized solid-phase material and the carbonized liquid-phase material in the carbonized solid-liquid-gas mixture.

[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 heavy metals from the carbonized liquid phase product using physical methods (such as adsorption methods) and / or chemical methods known to those skilled in the art. Therefore, the heavy metal separation device can be a heavy metal physical separation device and / or a heavy metal chemical separation device.

[0052] As an example, the heavy metal separation device is provided with an adsorbent or 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 the embodiments of the present application, the hydrothermal carbonization system further comprises one or more than one conveying device to convey one, two or three of the gaseous phase material, the solid phase material and the gaseous phase material described above to the corresponding device in the hydrothermal carbonization system for processing. Preferably, such a conveying device can be provided between every two devices. Those skilled in the art should understand that such a conveying device is known in the art, and the present application does not have a special limitation on the specific structure of the conveying device, as long as it can effectively convey the material to the desired device.

[0056] According to the embodiments of the present application, when it is necessary to cool the material, circulating water can be selected for cooling. For this purpose, the cooling device of the present application can also be provided with a pipeline for circulating cooling water.

[0057] According to the embodiments of the present application, the temperature for depolymerization of the organic carbon-containing material in the depolymerization device can be about 230-240℃, and the depolymerization time can be about 5-30min.

[0058] According to the embodiments of the present application, the reaction temperature in the catalytic carbonization device can be about 150-230℃, such as 180-200℃; and the reaction time can be about 30-300min, for example, 60-120min.

[0059] According to the embodiments of the present application, the unit A can also comprise one, two or more pre-treatment devices for pre-treating (or referred to as "pre-processing") the organic carbon-containing material before depolymerization. For example, the pre-treatment includes but is not limited to pre-processing such as crushing, pulping, depolymerization, extraction, soaking, etc. of the organic carbon-containing material.

[0060] According to the embodiments of the present application, the additive can be an additional additive required for reaction or processing in any one device in the unit A, such as one or more of a pH adjusting agent, 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 can be selected from a zeolite-based solid phase acid catalyst, such as a zeolite-based solid phase acid catalyst in the form of a powder catalyst or an oxygen carrier.

[0061] According to the embodiments of the present application, the solid acidic catalyst can 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 fine ash particles discharged during the combustion of fuel, optionally containing or not containing unburned carbonaceous particles. Unburned carbonaceous particles are 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, and more preferably, all of the fly ash is 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 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.

[0065] It should be understood by those skilled in the art that when a dispersant is used, the dispersant can 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 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 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, or 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 can 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%, or 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 the embodiment of the present utility model, the oxygen carrier is prepared from fly ash as raw material through a fusion polymerization (melt polymerization)-hydrothermal double-stage alkali conversion method.

[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 the 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 the 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, 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, and the inorganic base may be selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, and / or ammonium hydroxide.

[0085] According to an embodiment of the present utility model, the solid acid catalyst may be the nanocomposite zeolite material described in Chinese patent application No. 202310381676.9.

[0086] According to an embodiment of the present invention, the nano-scale crystal structure of the nano-composite zeolite material is a FAU / Zeolite structure, preferably a FAU / Zeolite Y 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, ferric chloride) as raw materials.

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

[0091] According to the embodiment of the present utility model, the nano-composite zeolite material has a three-level pore structure: the pore diameter of the first-level pore structure does not exceed 10nm, for example, does not exceed 5nm, and is preferably less than 2nm (i.e., micropores); the pore diameter of the second-level pore structure (also called mesopores) is equal to or greater than the pore diameter of the first-level pore structure, and does not exceed 50nm; the pore diameter of the third-level pore structure (also called macropores) is greater than 50nm, for example, greater than 50nm and not more than 500nm, such as 200nm.

[0092] According to the embodiment of the present invention, the sum of the specific surface areas of the nanocomposite zeolite material is 150 to 1500 m 2 / g, for example, 300 to 1200 m 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 accounts for more than 50%, for example, more than 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 performance (water-holding performance 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 insoluble in alkali (high pH) and acid (low pH).

[0098] According to the 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 fields, etc., such as fly ash from fly ash landfills and ultrafine powder raw materials prepared from boiler combustion residues; preferably, fly ash generated immediately by the pulverized coal boiler of the power plant is selected.

[0099] According to an embodiment of the present invention, each device in the unit A may optionally be independently provided with a feed port for feeding additives. Preferably, the pre-treated organic carbon-containing material is mixed with the additive and then fed into the depolymerization device for reaction; alternatively, the pre-treated organic carbon-containing material and the additive are mixed in the depolymerization reaction device and then reacted.

[0100] According to an embodiment of the present invention, the additive is a dispersion with a zeolite-based carrier and the 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. Preferably, after the hydrothermal carbonization reaction, the zeolite-based primary dispersion of the additive is further dispersed in water coke.

[0102] According to the embodiment of the present utility model, the weight ratio of the material containing organic carbon as a raw material to the additive (such as a solid acid catalyst) can be 100:1 to 1:1, such as 10:1 to 2:1, preferably 6:1 to 4:1, and more preferably 5:1.

[0103] According to the embodiment of the present utility model, preferably, when the weight ratio of the material containing organic carbon as a raw material to the additive (such as a solid acid catalyst) is 6:1 to 4:1, more preferably 5:1, the reaction temperature of the depolymerization device and / or the catalytic carbonization device can be reduced to an average of 150 to 180°C, such as 170°C; and / or, the reaction time of the depolymerization device and / or the catalytic carbonization device can be reduced to 30 to 120 minutes, for example, 20 to 60 minutes.

[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 suit 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).

[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 a filter press, drying and / or granulation device.

[0111] According to an embodiment of the present invention, the unit B includes a combustion device or an incineration device, which can 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 the waste heat furnace, the desulfurization device, and the dust collector connected in sequence, and the flue gas discharged from the combustion furnace is treated in sequence through waste heat recovery, desulfurization, and dust removal.

[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 includes 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 CO2-enriched and nitrogen-free atmosphere in the furnace, and the second branch produces CO2-enriched gas, which is output as carbon sequestration or CO2 gas raw material for industrial use.

[0116] According to the embodiment of the present utility model, the combustion device further comprises a combustion furnace flue gas circuit, which is connected in parallel with the backup oxygen supply device pipeline 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 melting 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 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 reagent inlet.

[0121] According to the embodiment of the utility model, the unit C further comprises a filtering device, the filtering device liquid outlet is connected with the dilution tank through a pipeline, and the medium liquid obtained by filtering is recycled.

[0122] According to the embodiment of the utility model, the additive is prepared by a melt-aggregation and hydrothermal double-stage alkali conversion method using fly ash as raw material.

[0123] According to the embodiment of the utility model, the preparation method of the additive comprises the following steps: melt-aggregation (also referred to as "alkali melting") of fly ash under alkaline conditions, grinding of the obtained polymer, dilution, ultrasonic treatment, hydrothermal activation reaction, and obtaining of the oxygen carrier.

[0124] According to the embodiment of the utility model, the alkaline condition can be provided by a strong base, for example, the strong base is potassium hydroxide and / or sodium hydroxide.

[0125] According to the embodiment of the utility model, the melt-aggregation condition comprises: a temperature of 400-650 DEG C and a time of 2-8h; for example, a temperature of 450-550 DEG C and a time of 4-6h.

[0126] According to the embodiment of the utility model, the polymer is ground to 0.075mm-0.2mm.

[0127] According to the embodiment of the utility model, the concentration of solid substances in the obtained mixture after dilution is 1-5mol / L, for example, 2.5mol / L.

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

[0129] According to the embodiment of the utility model, fly ash is optionally added or not added to the mixture during dilution.

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

[0131] According to the embodiment of the utility model, the hydrothermal activation reaction condition comprises: a temperature of 70-100 DEG C and a time of 2-8h; for example, a temperature of 80-90 DEG C and a time of 4-8h.

[0132] Alternatively, the preparation method of the additive comprises the following steps: a zeolitization process of fly ash through a two-stage synthesis (melt, hydrothermal) process, and preparation of the nano-composite zeolite material.

[0133] According to the embodiment of the utility model, the melt stage process comprises: mixing of fly ash and alkali, heating and melting, grinding, dilution, and obtaining of 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 the 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 start of the hydrothermal process with N>1, 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 the 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 crystallization 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 the 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 utility model, the solid acid catalyst may be the fly ash zeolite-based composite nano oxygen carrier described in Chinese patent application No. 202311217726.6.

[0146] According to embodiments of the present application, the fly ash is a fine ash particle emitted during a fuel combustion process, optionally including or not including unburnt carbonaceous particles, also known as pulverized coal ash or soot. In preferred embodiments, the fly ash is a boiler combustion fly ash, such as fly ash produced by unit B, more preferably all of the fly ash is derived from fly ash produced by unit B.

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

[0148] According to embodiments of the present application, the oxygen carrier comprises a metal oxide and a support, wherein the support is a fly ash zeolite-based support. Preferably, the metal oxide is dispersed in the support. For this purpose, a powder form of the metal oxide or a metal oxide comprising a dispersing agent can be used to disperse it in the support. For example, a fly ash zeolite-based microporous aluminosilicate crystal, the metal oxide is uniformly distributed (or dispersed) in the crystal structure of the support.

[0149] It will be appreciated by those skilled in the art that when a dispersing agent is used, the dispersing agent can be selected from dispersing agents known to those skilled in the art, as long as it helps to disperse the metal oxide in the support.

[0150] According to embodiments of the present application, the oxygen carrier has a crystal structure of a FAU zeolite.

[0151] According to embodiments of the present application, the metal oxide includes, but is not limited to, an oxide of one selected from the group consisting of potassium, sodium, magnesium, iron, zinc, chromium, manganese, cobalt, nickel, copper, aluminum, lead, manganese, zirconium, tin, zinc, tungsten, molybdenum, and vanadium; preferably, an iron oxide, a zinc oxide, an aluminum oxide; as an example, the metal oxide is diiron trioxide, zinc oxide, aluminum oxide.

[0152] According to embodiments of the present application, when the metal oxide is diiron trioxide, it can have a nanocrystalline particle structure of γ-Fe2O3, α-Fe2O3, γ-Fe3O4.

[0153] According to embodiments of the present application, the metal of the metal oxide is derived from a metal contained in the fly ash itself, or an additional metal or metal oxide. For example, the metal contained in the fly ash itself is derived from a metal in a material containing organic carbon.

[0154] Those skilled in the art will appreciate that, upon startup of the chemical looping combustion system, metals or metal oxides can be added to the fly ash in unit C as needed to ensure that the solid acid catalyst contains a sufficient amount of metal oxide. However, once the chemical looping combustion system is in steady-state operation, as the metal elements circulate within the combustion system through oxidation and reduction reactions, there is no need to add additional metals or metal oxides. To this end, units A, B, C, and D of the combustion system of the present invention are each sealed, and the connecting pipelines between A, B, C, and D are also sealed, 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, or 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 can 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%, or 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 the embodiment of the present utility model, the oxygen carrier is prepared from fly ash as raw material through a fusion polymerization (melt polymerization)-hydrothermal double-stage alkali conversion method.

[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 the embodiment of the present application, 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) and / or cerium (Ce) element, preferably the cerium element; for example, the semi-metal element is silicon (Si).

[0164] According to the embodiment of the present application, the metal complex can also be selected from ruthenium, nickel, palladium, silver, platinum, nickel, cobalt, vanadium, aluminum, chromium, copper, zinc, molybdenum, tin, manganese, gold, rhodium, zirconium, tungsten, rhenium, osmium, iridium, titanium and the like metal compounds, preferably the compound of aluminum and / or zinc, more preferably aluminum oxide and / or 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 (for example, silicon dioxide).

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

[0167] According to the embodiment of the present application, the metal complex is a nano-sized metal oxide, for example, nano-sized cerium oxide, nano-sized aluminum oxide and / or nano-sized zinc oxide.

[0168] According to the embodiment of the present application, the size of the metal oxide nanoparticles and / or metal complex is less than 300 nm, preferably less than 200 nm, more preferably less than 100 nm, and still preferably less than 30 nm, 10 nm, 4 nm.

[0169] According to the embodiment of the present application, the oxygen carrier can also contain an additive. For example, the additive is one or more of inorganic acid, inorganic base and the like. For example, the inorganic acid can be selected from hydrochloric acid, nitric acid, sulfuric acid and / or phosphoric acid and the like, and the inorganic base can be selected from sodium hydroxide, potassium hydroxide, calcium hydroxide and / or ammonium hydroxide and the like.

[0170] As an example, glycolic acid as one of the dispersants helps to prevent or at least delay the agglomeration of nanoparticles and the deactivation of the catalyst, which can improve the combustion efficiency.

[0171] According to the embodiment of the present application, the solid acid catalyst can be the nano-composite zeolite material as described in Chinese Patent Application 202310381676.9.

[0172] According to the embodiment of the present application, the nano-composite zeolite material has a nano-sized crystal structure of FAU / Zeolite structure, preferably a FAU / Zeolite Y type structure.

[0173] According to the embodiment of the present application, the nano-composite zeolite material has a micro-mesoporous cage frame void space.

[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, ferric chloride) as raw materials.

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

[0177] According to the embodiment of the present utility model, the nano-composite zeolite material has a three-level pore structure: the pore diameter of the first-level pore structure does not exceed 10nm, for example, does not exceed 5nm, and is preferably less than 2nm (i.e., micropores); the pore diameter of the second-level pore structure (also called mesopores) is equal to or greater than the pore diameter of the first-level pore structure, and does not exceed 50nm; the pore diameter of the third-level pore structure (also called macropores) is greater than 50nm, for example, greater than 50nm and not more than 500nm, such as 200nm.

[0178] According to the embodiment of the present invention, the sum of the specific surface areas of the nanocomposite zeolite material is 150 to 1500 m 2 / g, for example, 300 to 1200 m 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 accounts for more than 50%, for example, more than 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 performance (water-holding performance 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 insoluble in alkali (high pH) and acid (low pH).

[0184] According to the 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 fields, etc., such as fly ash from fly ash landfills and ultrafine powder raw materials prepared from boiler combustion residues; preferably, fly ash generated immediately by the pulverized coal boiler of the power plant is selected.

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

[0186] According to the embodiment of the present utility model, 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 organic carbon-containing material after pre-treatment.

[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, thereby mixing it with the pre-treated organic carbon-containing material.

[0190] The utility model 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 utility model also provides a method for generating electricity, comprising using the combustion system or the integrated system to generate electricity, for example, using the combustion system to process materials containing organic carbon, and using the power generation system to generate electricity.

[0193] The utility model also provides a method for processing materials containing organic carbon, which comprises using the combustion system to process the materials containing organic carbon.

[0194] The utility model 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 a high-activity solid acid catalytic zeolite material 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 a catalyst, the hydrothermal process synthesizes low-value biomass feedstock into a high-calorific-value water coke fuel carrying a large amount of heterogeneous metal catalytic combustion-supporting oxygen carriers. The water coke, a high-quality fuel carrying a large amount of heterogeneous metal catalytic combustion-supporting oxygen carriers, then enters the boiler combustion atmosphere, where it is introduced into the fuel gas molecules in the boiler atmosphere, causing catalytic combustion on the surface of the highly active metal particles. The ashes after combustion then react with air to reform oxide-rich fly ash. Therefore, the technical approach for in-situ resource utilization of fly ash designed in this utility model constructs a cyclical circuit for the oxidation, zeolization, and reduction of the combustion ash metals, forming an "oxidation, synthesis, and reduction" chemical chain cycle architecture for oxygen-carrying catalytic materials, and creating a chemical chain boiler combustion technology for efficient biomass thermal power systems. While the fly ash solid waste metals are recycled and utilized as resources, the catalytic process enhances the efficiency of the biomass hydrothermal carbonization reaction, and the catalytic process improves the oxidation efficiency of the water coke boiler combustion.

[0197] Among them, the utility model uses the residual fly ash from the combustion of biomass thermal power boilers, synthesizes it into a zeolite-based solid acid catalytic material in situ, and serves as a dual-function catalyst in situ to improve the efficiency of the "hydrothermal carbonization / hydrocarbon combustion" process in the new biomass thermal power system.

[0198] To avoid blockage at the reactor inlet and outlet caused by the addition of large doses of catalytic material and to avoid production bottlenecks in biomass-to-carbon conversion, the C-HTC unit described in this utility model has been upgraded. The flow control of the pump used for continuous reactant processing has been replaced with a spiral-propulsion flow control system, and the carbonization reactor has been converted from a vertical to a horizontal tube carbonization reactor. The catalytic reaction of the biomass in the C-HTC spiral-propulsion carbonization reactor horizontal tube unit produces a fly ash zeolite-based heterogeneous metal-loaded solid acid catalytic material. This product also establishes a "feedback" loop for the output of the C-HTC catalytic carbonization material to the biomass feedstock through a secondary dispersion process, further improving the efficiency and yield of biomass conversion to solid water coke.

[0199] The functional layout of the in-situ production of fly ash zeolite-based catalytic materials in the utility model has pioneered a nanotechnology approach to thermochemical catalytic efficiency enhancement in the process of biomass thermoelectric conversion, realized 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 utility model designs the fly ash zeolite-based solid acid catalyst with 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 a zeolite-based catalytic material in situ of the system. The material serves 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 the 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 regenerated material for dual-phase catalysis, which simplifies the complexity of the industrial process and reduces the cost of the system. This utility model can upgrade a traditional carbonaceous fuel boiler power generation system to an advanced chemical looping combustion power generation system while retaining the core equipment of a mature carbonaceous fuel boiler power generation system with only minor modifications. This overcomes the technical difficulty of upgrading existing boiler systems due to the differences between the CLC system, which is based on a dual-interconnected fluidized bed gas-solid reactor process prototype and the existing boiler equipment of most coal-fired power generation units worldwide. This provides an economically feasible technical approach for upgrading and transforming traditional biomass thermal power systems deployed on a large scale in China to advanced chemical looping combustion power generation systems. BRIEF DESCRIPTION OF THE DRAWINGS

[0201] Figure 1 This is a schematic diagram of the biomass thermoelectric system of the utility model;

[0202] The meanings of the figures are as follows: A1-municipal 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 extractor; 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 extractor; B19-pressing machine; B20-slag box; B21-transportation of impurities; B22-flushing water; B23-sand and impurity removal; B24-grease separator; B25-solid-liquid separation; B26-municipal feces; B27-integrated impurity removal equipment; B28-discharge tank; B29-low-level water tank; B30-flushing water; B31-transportation of impurities.

[0204] C1-Mixing tank; C2-Distribution screw; C3-Pin drum metering device; C4-Heating screw; C5-Feeding screw; C6-T-tube; C7-Cooking tube; C8-Slurry separation; C9-Automatic sedimentation centrifuge; C10-Pelletizing 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 and hemicellulose slurry; C31-backflush cyclone; C32-steam; C33-secondary dispersion circuit; C34-external circulating water; C35-external circulating water; C36-solids; C37-barreling; 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 fly ash; E3 - NaOH storage tank with vibrator; E4 - Screw conveyor for 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 - Stirrer; E12 - Heater; E13 - Hydrothermal activation; E14 - Filter press; E15 - External water; E16 - Washing; E17 - Zeolite-based nanocomposite material for fly ash; E18 - Add one-third of the total amount of raw ash; E19 - Fly ash storage tank with vibrator; E20 - Screw conveyor for fly ash ; E21-screw conveyor for transporting fly ash; E22-fly ash and other raw material storage tanks with vibrators; E23-screw conveyor for transporting fly ash; E24-NaOH storage tank with vibrators; 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-NaOH aqueous solution; E37-alkaline water reuse; E38-external water; E39-alkaline water reuse.

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

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

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

[0210] Figure 5 This is the principle diagram of traditional chemical looping combustion.

[0211] Figure 6 This is the principle diagram of chemical loop combustion of this utility model.

[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 thermoelectric 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 merely exemplary illustrations and explanations of the present invention and should not be construed 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, comprising:

[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 includes a catalytic carbonization device, or includes 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 depolymerization device and then by the catalytic carbonization device; alternatively, the material can be directly processed by the catalytic carbonization device.

[0227] Placing the catalytic carbonization device downstream of the depolymerization device may include not only directing the material output from the depolymerization device through the catalytic carbonization device for treatment, but also directing the material into the catalytic carbonization device for treatment, or first subjecting the material output from the depolymerization device to treatment by other devices before being subjected to the catalytic carbonization device for treatment. The above-mentioned different methods should all be understood as optional methods encompassed by "the catalytic carbonization device is disposed downstream of the depolymerization device." Therefore, according to the embodiments of the present invention, the depolymerization device and the catalytic carbonization device may be directly connected 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 to the depolymerization device. For example, the feeding device is a feeding device for a solid-liquid mixture material.

[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 waste, kitchen waste, sewage treatment sludge, water sediment, landfill leachate, wood waste, and crop straw.

[0231] The deagglomeration device may be provided with at least one feed port, so that the material provided by the feed device enters the deagglomeration device.

[0232] The material in the feeding device can directly enter the depolymerization device. Alternatively, a raw material mixer, a preheating mixer, and / or a mixing liquid storage tank can be provided between the feeding device and the depolymerization device, so that the material in the feeding device passes through the raw material mixer, the preheating mixer, and / or the mixing 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 additives may also enter the depolymerization device through the feed port of the solid-liquid mixture, as long as they can participate in the depolymerization reaction.

[0238] The depolymerization device may further be provided with at least one outlet for depolymerized gaseous materials and at least one outlet for depolymerized non-gaseous materials.

[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 and liquid materials that are processed by a depolymerization device and need to be further processed in a buffer separation device and / or a catalytic carbonization 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 gaseous material can be mixed with the material provided by the feeding device, for example, it can be mixed with the material provided by the feeding device in a raw material mixer.

[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 enters the catalytic carbonization device.

[0245] 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.

[0246] 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.

[0247] The catalytic carbonization device may also be provided with at least one outlet for carbonized gaseous material and at least one outlet for carbonized solid-liquid-gas mixture material. Preferably, the outlet for carbonized gaseous 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 gaseous 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 outlet for carbonized gaseous material and at least one outlet for carbonized solid-liquid-gas mixture material. Preferably, the outlet for the carbonized gaseous 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 gaseous material.

[0250] The condensate obtained by cooling the carbonized gas phase material can be mixed with the material provided by the feeding device, for example, it can be mixed with the material provided by the feeding device in the raw material mixer. Therefore, the carbonized gas phase processing device can be connected to the raw material mixer through a liquid phase conveying pipeline.

[0251] The carbonization gas phase treatment device can 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.

[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 heavy metals from the carbonized liquid phase product using physical methods (e.g., adsorption methods) and / or chemical methods known to those skilled in the art. Therefore, the heavy metal separation device can be a physical heavy metal separation device and / or a chemical heavy metal separation device.

[0257] As an example, the heavy metal separation device is provided with an adsorbent or 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 further provided with a heat recovery device to utilize 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 also includes one or more conveying devices to convey one, two, or three of the aforementioned gaseous materials, solid materials, and vapor materials to the corresponding devices in the hydrothermal carbonization system for processing. Preferably, such a conveying device can be provided between each two devices. Those skilled in the art will appreciate that such conveying devices are known in the art, and therefore, the present invention does not particularly limit the specific structure of the conveying device, as long as it can effectively convey the material to the desired device.

[0261] When needs cool down material, can select to use circulating water to cool down. For this reason, cooling device of the present utility model can also be provided with the pipeline that is used for circulating cooling water.

[0262] The unit A can be used to treat materials containing organic carbon, such as municipal waste (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 municipal waste, domestic waste, restaurant waste, kitchen waste, municipal feces, sewage treatment sludge, water body sediment, landfill 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 minutes.

[0264] The reaction temperature in the catalytic carbonization device can be about 150-230° C., such as 180-200° C.; the reaction time can be about 30-300 min, such as 60-120 min.

[0265] The unit A may further 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, depolymerizing, extracting, soaking, and the like.

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

[0267] Each device in the unit A may optionally be independently provided with a feed port for feeding additives. Preferably, the pre-treated organic carbon-containing material is mixed with the additive and then fed into the depolymerization device for reaction; alternatively, the pre-treated organic carbon-containing material and the additive are mixed in the depolymerization reaction device and then reacted.

[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 organic carbon-containing material as a raw material to the additive (such as a solid acid catalyst) can be 100:1 to 1:1, such as 10:1 to 2:1, preferably 6:1 to 4:1, 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 minutes, for example, 20 to 60 minutes.

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

[0272] The product of unit A can be filtered, dried and / or pelletized to prepare a catalytic combustion-supporting fuel product. Preferably, the particle size of the catalytic combustion-supporting fuel product can be adjusted to meet the requirements or standards of subsequent units.

[0273] The unit A may further comprise 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 can 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 the waste heat furnace, desulfurization device, and dust collector connected in sequence, and the flue gas discharged from the combustion furnace is treated in sequence through waste heat recovery, desulfurization, and dust removal.

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

[0281] The combustion device further comprises 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 CO2-enriched and nitrogen-free atmosphere in the furnace, and the second branch produces CO2-enriched gas, which is output as carbon sequestration or CO2 gas raw material for industrial use.

[0283] The combustion device also includes a combustion furnace flue gas circuit, which is connected in parallel with the backup oxygen supply device pipeline for blowing 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 includes 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 further comprises a filtering device, the liquid outlet of the filtering device is connected to a dilution tank via a pipeline, and the medium liquid obtained by filtration is recovered 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: melting fly ash under alkaline conditions (also known as "alkali melting"), grinding the obtained polymer, diluting it, ultrasonically treating it, and subjecting it to hydrothermal activation reaction to obtain the oxygen carrier.

[0291] The alkaline condition can be provided by a strong base, for example, 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 is ground to 0.075mm-0.2mm.

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

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

[0296] The fly ash is optionally added or not added to the dilution.

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

[0298] The conditions of the hydrothermal activation reaction include: temperature 70-100℃, time 2-8h; for example, temperature 80-90℃, time 4-8h.

[0299] Alternatively, the preparation method of the additive comprises the following steps: fly ash is subjected to a two-stage synthesis of zeolitization by fusion and hydrothermal reaction to obtain the nanocomposite zeolite material.

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

[0301] The alkali is selected from strong alkalis, for example sodium hydroxide.

[0302] The heating and melting temperature can be 500-600℃, and the time can be 1-9h.

[0303] The process of the hydrothermal stage comprises: aging and hydrothermal process to obtain crystals; or comprises: adding doping elements, aging and hydrothermal process to obtain crystallized composite element crystals.

[0304] The hydrothermal stage can comprise repeated hydrothermal processes of adding N doping elements, N being an integer equal to or greater than 1, for example N=1, 2, 3, 4, 5, 6, 7, 8, 9, 10.

[0305] The doping elements are preferably added before the start of the hydrothermal process when N>1, to introduce specified elements so that these elements uniformly form high-activity catalytic sites.

[0306] The doping elements are introduced by the following dopants, including but not limited to nanoparticles, alkalis and / or crystal nucleus materials of the one, two or more doping elements.

[0307] The dopants are added to the crystallization precursor solution, but the preparation of the crystallization precursor solution is different when N=1 and N≥2:

[0308] When N = 1, the crystalline precursor solution is obtained by mixing fly ash with a base, or further mixing with a dopant, heating to melt, grinding, and dilution;

[0309] When N ≥ 2, the crystalline precursor solution is obtained by mixing the filtrate obtained after the previous hydrothermal crystallization stage with a dopant, and optionally adding a base, mixing and diluting.

[0310] The mass ratio of the dopant to the crystalline 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 2-48h.

[0312] According to the embodiments of the present application, the solid acid catalyst can be a fly ash zeolite-based composite nano oxygen carrier as described in Chinese patent application 202311217726.6.

[0313] According to the embodiments of the present application, the fly ash is a tiny ash particle discharged during the fuel combustion process, optionally containing or not containing unburned carbonaceous particles, and is also known as fly ash or soot when containing unburned carbonaceous particles. In preferred embodiments, the fly ash is a boiler combustion fly ash, for example, fly ash generated by unit B, and more preferably, all of which is derived from fly ash generated by unit B.

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

[0315] According to the embodiments of the present application, 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 comprising a dispersant can be used to disperse it in the carrier. For example, a fly ash zeolite-based microporous aluminosilicate crystal, and the metal oxide is uniformly distributed (or dispersed) in the crystal structure of the carrier.

[0316] The skilled person will appreciate that when a dispersant is used, the dispersant can be selected from dispersants known to the skilled person, as long as it helps to disperse the metal oxide in the carrier.

[0317] According to the embodiments of the present application, the oxygen carrier has a crystal structure of FAU zeolite.

[0318] According to the embodiment of the present application, the metal oxide includes but is not limited to the oxide of one selected from the following metals: potassium, sodium, magnesium, iron, zinc, chromium, manganese, cobalt, nickel, copper, aluminum, lead, manganese, zirconium, tin, zinc, tungsten, molybdenum and vanadium; preferably iron oxide, zinc oxide, aluminum oxide; as an example, the metal oxide is ferroferric oxide, zinc oxide, aluminum oxide.

[0319] According to the embodiment of the present application, when the metal oxide is ferroferric oxide, it can have a nano-crystalline particle structure of γ-Fe2O3, α-Fe2O3, γ-Fe3O4.

[0320] According to the embodiment of the present application, the metal of the metal oxide is derived from the metal contained in the fly ash itself, or an additional 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 at the start of the chemical looping combustion system, metal or metal oxide can be added to the fly ash in unit C as needed to make the solid acid catalyst have a sufficient amount of metal oxide. However, when the metal elements are circulated in the combustion system through oxidation and reduction reactions after the chemical looping combustion system is in a steady state operation, there is no need to add additional metal or metal oxide. For this purpose, units A, B, C and D of the combustion system of the present application are each closed, and the connecting pipelines between A, B, C and D are closed, so as to reduce or avoid unnecessary consumption of metal elements.

[0322] According to the embodiment of the present application, the metal oxide can be a nano-particle. For example, the size of the nano-particle is 0.1-100 nm, such as 1-50 nm, and exemplary values are 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50 nm.

[0323] According to the embodiment of the present application, the metal oxide nano-particle is a ferroferric oxide nano-particle with a particle size of 3-5 nm.

[0324] According to the embodiment of the present application, the particle shape of the metal oxide can be circular, ellipsoidal or other regular or irregular shape.

[0325] According to the embodiment of the present application, the oxygen carrier is a micro-nano material, i.e. having a micro-nano level crystal structure.

[0326] According to the embodiment of the present application, the mass ratio of the metal oxide to the oxygen carrier is 5-35 wt%, such as 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%.

[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 the embodiment of the present utility model, the oxygen carrier is prepared from fly ash as raw material through a fusion polymerization (melt polymerization)-hydrothermal double-stage alkali conversion method.

[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 the 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 the 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, 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, and the inorganic base may be selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, and / or ammonium hydroxide.

[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 combustion efficiency.

[0337] According to the embodiment of the present application, the solid acid catalyst can be the nano-composite zeolite material as described in Chinese patent application 202310381676.9.

[0338] According to the embodiment of the present application, the nano-scale crystal structure of the nano-composite zeolite material is FAU / Zeolite structure, preferably FAU / Zeolite Y type structure.

[0339] According to the embodiment of the present application, the nano-composite zeolite material has micro-mesoporous cage frame void space.

[0340] According to the embodiment of the present application, the nano-composite zeolite material is an aluminosilicate hydrate.

[0341] According to the embodiment of the present application, the nano-composite 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 nano-composite zeolite material in the form of their chlorides (e.g. zinc chloride, iron chloride) as raw materials.

[0342] According to the embodiment of the present application, the nano-composite zeolite material is a rich-Jarosite zeolite type structure (FAU).

[0343] According to the embodiment of the present application, the nano-composite zeolite material has a three-level pore structure: the pore size of the first-level pore structure is not more than 10 nm, for example not more than 5 nm, and is preferably less than 2 nm (i.e. microporous); the pore size of the second-level pore structure (also known as mesoporous) is equal to or greater than the pore size of the first-level pore structure, and is not more than 50 nm; the pore size of the third-level pore structure (also known as macroporous) is greater than 50 nm, for example greater than 50 nm and not more than 500 nm, such as 200 nm.

[0344] According to the embodiment of the present application, the sum of the specific surface areas of the nano-composite zeolite material is 150-1500 m 2 / g, for example 300-1200 m 2 / g, and also 500-1000 m 2 / g.

[0345] According to the embodiment of the present application, the cation exchange capacity (CEC, Cation Exchange Capacity) of the nano-composite zeolite material is 150-250 cmol(+) / kg.

[0346] According to the embodiment of the present application, the pore volume ratio of the nano-composite zeolite material is more than 50%, for example more than 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 performance (water-holding performance 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 insoluble in alkali (high pH) and acid (low pH).

[0350] According to the 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 fields, etc., such as fly ash from fly ash landfills and ultrafine powder raw materials prepared from boiler combustion residues; preferably, fly ash generated immediately by the pulverized coal boiler of the power plant 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, thereby mixing it with the pre-treated organic carbon-containing material.

[0356] Example 2

[0357] This embodiment provides another combustion system, which differs from Example 1 only in that the additive is selected from the nanocomposite zeolite material described in Chinese patent application 202310381676.9.

[0358] Example 3

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

[0360] The above examples illustrate the specific implementation methods of the present invention. However, the scope of protection of the present invention is not limited to the above-mentioned exemplary implementation methods. Any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art within the spirit and principles of the present invention shall be included in the scope of protection of the claims of the present invention.

Claims

1. An integrated system, characterized in that: include: A combustion system and a power generation system, wherein the H2O, CO2 and hot air generated by the combustion system are output to generate electricity through heat exchange; The combustion system comprises: Unit A for catalytic hydrothermal carbonization; said unit A comprises a depolymerization device and a catalytic carbonization device disposed downstream of said depolymerization device; the product of said unit A is subjected to filter pressing, drying and / or granulation to prepare a catalytic combustion-supporting fuel product; a unit B located downstream of the unit A and used for combustion; The unit B includes a combustion device or an incineration device; The combustion device includes a flue gas treatment module connected to the combustion furnace, and the flue gas treatment module includes a waste heat furnace, a desulfurization device and a dust collector connected in sequence. The flue gas discharged from the combustion furnace is processed in sequence through waste heat recovery, desulfurization and dust removal and cleaning steps; the combustion device also includes a circulation loop for clean flue gas to enter the furnace and an air preheater; In the unit B, combustion or incineration is carried out in the presence of the product of the unit A; A unit C located downstream of the unit B and used to prepare the additive in the unit A; The additive is a solid acidic catalyst or an oxygen carrier, and the solid acidic catalyst or the oxygen carrier comprises a metal oxide and a carrier, and the metal oxide is dispersed in the carrier; and The additive produced by unit C is conveyed to the transfer unit D of unit A.

2. The integrated system according to claim 1, wherein: The unit A further comprises a spiral flow controller to promote the reaction in the depolymerization device and / or the catalytic carbonization device.

3. The integrated system according to claim 1 or 2, characterized in that: The depolymerization device and / or catalytic carbonization device is a horizontal tube reaction device.

4. The integrated system according to any one of claims 1 to 2, characterized in that: in: The unit C is used to prepare the additive in the unit A, and the solid acid catalyst is prepared by alkali melting and hydrothermal zeolite treatment of fly ash; The fly ash comes from the fly ash generated by the combustion or incineration of unit B.

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