Reactor for low-temperature catalytic decomposition of oxycarbide and preparation method and system thereof

Abstract

The invention provides a reactor for low-temperature catalytic decomposition of oxycarbide and a preparation method and system thereof. The reactor is a spherical reactor with the diameter larger than 15 mm, macropores and mesopores are distributed in the surface and the interior of the reactor, catalysts are loaded in the macropores and the mesopores, the specific surface area of the reactor is 1.00-2.00 m < 2 > / g, and the number of the pores in the reactor is 1.00 * 10 < 11 >-2.00 * 10 < 11 >. The reactor for low-temperature catalytic decomposition of oxycarbide is designed and prepared, a bed layer formed by a plurality of spherical reactors decomposes CO2 and CO in industrial flue gas into harmless substances such as C, O2 and the like at the low temperature of 160-180 DEG C through the synergistic effect of a double-activity adsorption and catalysis integrated system, a binary porous structure and a multi-layer empty volume structure.

Description

Technical Field

[0001] The present invention relates to the technical field of environmental protection air treatment, and particularly to a reactor for low-temperature catalytic decomposition of carbon oxides, a preparation method thereof, and a system thereof. Background Art

[0002] Under the current practical technical background of reducing carbon emissions and delaying the rise of environmental temperature, the treatment of carbon dioxide (CO2) emissions has become an important technical challenge. However, there is currently no technically feasible solution with a reasonable cost-effectiveness ratio for the treatment of carbon dioxide emissions. Most existing solutions have drawbacks such as high costs, serious secondary pollution, poor safety, and inconvenience for commercial promotion, such as carbon capture and storage technology (CCS), biological plant conversion technology, adsorption technology, etc. However, there is currently no technically feasible solution with a reasonable cost-effectiveness ratio for the treatment of carbon dioxide emissions. Most existing solutions have drawbacks such as high costs, secondary pollution, poor safety, and inconvenience for commercial promotion. Currently, there is no effective technology for low-temperature catalytic decomposition and removal of carbon oxides.

[0003] There is an urgent need to provide a reactor and system for low-temperature catalytic decomposition of CO2 and CO. Summary of the Invention

[0004] To solve the above technical problems, the present invention provides a reactor for low-temperature catalytic decomposition of carbon oxides, a preparation method thereof, and a system thereof, which are innovative special technologies for reducing carbon emissions. The reactor for low-temperature catalytic decomposition of carbon oxides designed by the present invention decomposes CO2 and CO in industrial flue gas into harmless substances such as C and O2 at a low temperature of 160-180°C. Compared with existing carbon capture technologies, biological plant conversion technologies, adsorption and other carbon reduction technologies, it has the advantages of high decarbonization efficiency, simple preparation, easy availability of materials, safe use, storage and transportation, simple operation, low investment and operation costs, long service life, no secondary pollution, and recyclability.

[0005] In a first aspect, the present invention provides a reactor for low-temperature catalytic decomposition of carbon oxides. The reactor is a spherical reactor with a diameter greater than 15 mm. Macropores and mesopores are distributed on the surface and inside of the reactor. The macropores and the mesopores are loaded with a catalyst. The specific surface area of the reactor is 1.00-2.00 m 2 / g, and the number of pores in the reactor is 1.00×10 11 -2.00×10 11 .

[0006] The present invention designs and prepares a reactor for low-temperature catalytic decomposition of carbon oxides (CO2 and / or CO), wherein a bed layer formed by multiple reactors is provided, and carbon oxides are decomposed by a dual-activity catalytic system, especially by utilizing the synergistic effect of its binary porous structure (macroporous, mesopores) and the multi-layer (bed layer, macropores and mesopores) empty volume structure formed by the bed layer stacked by the spherical reactors, CO2 and CO in the discharged industrial flue gas are decomposed into harmless substances such as C and O2 at a low temperature of 160-180°C.

[0007] Preferably, the diameter of the reactor is 20-40 mm.

[0008] Preferably, the macropores contain mesopores.

[0009] Preferably, the number of mesopores in the macropores is 3.00×10 5 -4.00×10 5 indivual.

[0010] In the present invention, the specific surface area of the mesopores is 100-2000nm 2 .

[0011] Preferably, the water absorption rate of the reactor is ≥50%.

[0012] In the present invention, the number of active points producing dual active centers in the mesopores reaches 4.00×10 4 -5.00×10 4 A mesoporous micro-reaction unit with fully inelastic collision and adsorption catalysis was established. This structure increases the number of pre-factors for the decomposition reaction of carbon oxides, reduces the bond energy of the broken bond (C=O), and reduces the decomposition activation energy to 120-150KJ / mol through dual-activity catalysis. This provides a kinetic basis for the catalytic reaction to achieve the decomposition and removal of CO2 and CO at 160-180℃.

[0013] Preferably, the mesoporous structure formed by the supported catalyst is an open pore structure and / or a cage group structure.

[0014] It is further preferred that the catalyst is a catalyst for low-temperature catalytic decomposition of (carbon oxides), preferably a dual-activity catalytic system for low-temperature catalytic decomposition of CO2 and CO. In the present invention, the catalyst for low-temperature catalytic decomposition of carbon oxides / dual-activity catalytic system for low-temperature catalytic decomposition of CO2 and CO can adopt catalytic materials known in the art. Dual activity is a single-activity catalytic system for converting carbon dioxide into carbon monoxide, and a single-activity catalytic system for low-temperature catalytic decomposition of carbon monoxide, thereby realizing the process of decomposing carbon dioxide into carbon monoxide, and low-temperature catalytic decomposition of carbon monoxide into carbon element and oxygen.

[0015] More preferably, the shape of the bed layer of the spherical reactor stack includes cylinder, cube, cuboid or irregular body.

[0016] Preferably, the empty volume of the bed of the spherical reactor stack is ≥60%. In the present invention, the reactor is a binary porous open structure, and the empty volume is the empty volume of multiple layers (bed, macropores and mesopores), that is, the empty volume between the reactors in the bed, and the empty volume of the macropores and mesopores in the reactor.

[0017] In the present invention, the catalyst for low-temperature catalytic decomposition of carbon oxides is a dual-activity catalytic system for low-temperature catalytic decomposition of CO2 and CO. Dual activity is an active catalytic system for decomposing carbon dioxide into carbon monoxide, and a catalytic system for low-temperature catalytic decomposition of carbon monoxide into C and O2, thereby achieving harmless treatment of carbon dioxide decomposition into carbon and oxygen, and the reaction is a secondary reaction. The catalytic reaction process is as follows.

[0018] Formula 1 Formula 2 The catalyst for low-temperature catalytic decomposition of carbon oxides / the dual-activity catalytic system for low-temperature catalytic decomposition of CO2 and CO adopts catalytic materials known in the art, and is optimized and matched for the first time in the present invention to form a dual-activity catalytic system for low-temperature catalytic decomposition of CO2 and CO, which is a first in China and abroad. In order to further improve the low-temperature catalytic decomposition effect, the present application has also optimized the catalytic material for many times, so that it has higher activity and efficiency in the low-temperature decomposition of carbon oxides in the reactor structure of the present invention.

[0019] Preferably, the reactor comprises the following raw materials in parts by weight: 40-50 parts of fly ash, 5-10 parts of dry clay, 5-15 parts of bentonite, 15-20 parts of main active precursor, 5-10 parts of auxiliary active precursor, 5-15 parts of binder, 5-20 parts of pore former, and 5-10 parts of adsorbent.

[0020] More preferably, fly ash is 40-50 parts, dry clay is 8-10 parts, bentonite is 5-8 parts, main active precursor is 15-18 parts, auxiliary active precursor is 5-8 parts, binder is 10-12 parts, pore former is 5-10 parts, and adsorbent is 5-8 parts.

[0021] Preferably, the main active precursor is manganese oxide, cerium oxide and copper oxide; preferably, the molar ratio of manganese oxide, cerium oxide and copper oxide is 4-7:3-5:0.5-2, preferably 6:4:1.

[0022] Preferably, the co-active precursor is selected from one or more of Fe2SO3, NiO, Nb2O5, MoO, TiO2 and ZrO.

[0023] Preferably, the fly ash is fly ash generated after the combustion of a chain grate furnace with bituminous coal as the main fuel. The fly ash includes, by weight content: SiO2: 40% - 60%, Al2O3: 25% - 45%, MgO: 2% - 5%, CaO: 1% - 4%, K2O: 1% - 3%, Fe2O3: 2% - 5%.

[0024] Preferably, the binder is CMC and / or flour.

[0025] Preferably, the pore former is selected from one or more of starch, pulverized coal, and epoxy resin.

[0026] Preferably, the adsorbent includes one or more of nickel oxide, magnesium oxide, niobium oxide, iron oxide, and titanium oxide.

[0027] In the present invention, the macroporous structure formed in the reactor is formed by low - molecular - weight organic substances volatilizing from the matrix during high - temperature calcination of starch, pulverized coal, or epoxy resin, etc., resulting in a large number of open macropores and channels. Carbon is precipitated during the high - temperature calcination of the non - linear polymers in the burned - out substances, forming a carbon layer on the surface of the macropores.

[0028] Preferably, the raw materials of the reactor further include an acid - leaching solution and / or a nitric acid solution. The concentration of the nitric acid solution is 25% - 30%; the acid - leaching solution is a nitric acid solution of a main active substance and a co - active substance. The main active substance is selected from one or more of copper nitrate, cerium nitrate, and manganese acetate, and the co - active substance is selected from one or more of ferrous sulfate, nickel nitrate, niobium nitrate, cobalt nitrate, and titanium nitrate. Further preferably, the main active substances are copper nitrate, cerium nitrate, and manganese acetate. Preferably, the molar ratio of Mn:Ce:Cu is 4 - 7:3 - 5:0.5 - 2, preferably 6:4:1. The co - active substances are ferrous sulfate, nickel nitrate, niobium nitrate, and cobalt nitrate with a molar ratio of 1 - 10:1 - 10:2 - 15:1 - 10, preferably 1:1:2:1. The weight ratio of the main active substance and the co - active substance in the acid - leaching solution is 20% - 25%, and the mass ratio of the main active substance to the co - active substance is 1 - 10:1, and the nitric acid concentration is 25% - 30%.

[0029] In a second aspect, the present invention provides a method for preparing the reactor for low - temperature catalytic decomposition of carbon oxides, including: 1) Matrix preparation: Mix the raw materials of the reactor, then let the mixture rest and ferment, then granulate and dry, and calcine the dried embryo to obtain the reactor matrix.

[0030] 2) Carrier casting: Immerse the reactor matrix in a nitric acid solution to obtain the reactor matrix after carrier casting.

[0031] 3) Load the main active substance and co-active substance: Immerse the reactor matrix after pelletizing the carrier in an acid leaching solution containing the main active substance and co-active substance, and then dry and calcine it.

[0032] Preferably, in step 1), the diameter of the spherical embryo after granulation is 20 - 40 mm; the drying is carried out by natural air drying at a temperature of 30 - 50 °C for 45 - 50 h, or drying at 100 - 120 °C for 2 - 5 h; the dried embryo is calcined at 800 - 980 °C for 5 - 20 h.

[0033] Preferably, in step 2), the concentration of the nitric acid solution is 20% - 40%, the soaking temperature is 30 - 50 °C, soak for 3 - 6 h by equal volume, and then dry at 100 - 200 °C for 3 - 5 h.

[0034] Preferably, in step 3), soak the reactor matrix after pelletizing the carrier by equal volume at 20 - 40 °C for 3 - 6 h, dry at 100 - 300 °C for 8 - 10 h, and calcine at 300 - 500 °C for 5 - 8 h.

[0035] In the present invention, raw materials such as fly ash, dry soil, bentonite, binder, pore-forming agent, main active precursor, co-active precursor, etc. are put into a mixer and fully mixed evenly under the action of equal volume of water as the medium.

[0036] In the present invention, the dosages of the acid leaching solution and the nitric acid solution are not limited, and the conventional dosages in the art can be used. For example, equal volume soaking can be used for the soaking in step 3).

[0037] In the present invention, after adding an appropriate amount of water to knead the clay into a ball with a diameter of 20 - 40 mm, a non-crystalline amorphous porous reactor between pottery and porcelain is prepared by high-temperature sintering in a furnace.

[0038] Preferably, the preparation device of the reactor includes a dryer, an ultrafine grinder, a mixer, a clay kneader, a granulator, a sintering furnace, an air cooler, a reaction kettle and a dryer; the mixer is connected to the clay kneader, the clay kneader is connected to the granulator, the granulator is connected to the dryer, the dryer is connected to the sintering furnace, the sintering furnace is connected to the reaction kettle, the reaction kettle is connected to the dryer, the air cooler is connected to the sintering furnace, the ultrafine grinder is connected to the mixer, and optionally the ultrafine grinder can also be connected to a second dryer.

[0039] More preferably, the mixer is a twin-screw mixer or a single-screw mixer; the clay kneader is a clay kneader for ceramic production; the granulator is an extruder or manual kneading; the sintering furnace is an electric high-temperature muffle furnace or a gas furnace.

[0040] In a third aspect, the present invention provides an application system for low-temperature catalytic decomposition of carbon oxides, which includes a decarbonization tower, and a smoke inlet pipe and a smoke outlet pipe connected to both ends of the decarbonization tower, wherein the decarbonization tower is provided with the above-mentioned reactor for low-temperature catalytic decomposition of carbon oxides. In the present invention, the decarbonization tower is used to place a reaction bed composed of a reactor and perform low-temperature catalytic decomposition of carbon oxides, and its shape, size and number of layers are designed and determined according to the flow rate of flue gas and the concentration of carbon oxides, so that the gas to be treated can enter through the smoke inlet pipe, pass through the bed better and perform catalytic decomposition, and be discharged by the smoke outlet pipe.

[0041] Preferably, the system further comprises an induced draft fan, a chimney direct exhaust bypass pipe and a stop valve; the induced draft fan is connected to the smoke outlet pipe, one end of the chimney direct exhaust bypass pipe is connected to the smoke outlet pipe, the other end of the chimney direct exhaust bypass pipe is connected to the smoke inlet pipe, and the stop valve is arranged on the smoke inlet pipe, the smoke outlet pipe and the chimney direct exhaust bypass pipe.

[0042] The reactor and system for low-temperature catalytic decomposition of carbon oxides designed by the present invention have a bed formed by multiple spherical reactors. Through the synergistic effect of the dual-active adsorption catalytic integrated system and the binary porous structure and the multi-layer empty volume structure, CO2 and CO in industrial flue gas are decomposed into harmless substances such as C and O2 at a low temperature of 160-180°C.

[0043] In the present invention, the decarbonization tower is used to place the reactor and perform low-temperature catalytic decomposition of carbon oxides. Its shape and size are comparable to the bed layer so that the gas to be treated can enter through the smoke inlet pipe, pass through the bed layer better and be catalytically decomposed, and be discharged from the smoke outlet pipe.

[0044] The present invention discloses a method for decomposing CO and CO2 into simple substances O2 and C at a low temperature of 160-180 degrees (the temperature for directly decomposing CO2 starts at 2500°C and is completely decomposed when it reaches 5000°C, with an activation energy of decomposition of more than 532 kJ / mol) through the reactor structure and catalytic action. This method is the result of synergistic effects from many aspects. The present invention obtains a specific reactor that can reduce the activation energy of carbon oxide decomposition by selecting materials and optimizing the ratio, and in particular designs a binary pore structure and a multi-layer empty volume open structure that reduce the decomposition activation energy. After multiple optimization and selection of processes and equipment, and nearly 6,000 repeated experiments, a low-temperature catalytic decomposition reactor of CO2 and CO was successfully prepared.

[0045] According to a preferred embodiment of the present invention, the reactor structure design and parameters include: the reactor design structure is a macroporous and mesoporous binary spherical structure, the sphere diameter is 20-40 mm, the specific surface area is 1.2-2.0 m 2 / g, the bulk density is 935-950 kg / m3, and the number of holes in each reactor is 1.5×10 11 -2×1011 The diameter of the macropores is 1600-1900 nm, and the number of mesopores formed in the macropores after loading the catalyst is 3.0×10 5 -4.0×10 5 The mesopore diameter is 20-30nm, the multilayer void volume is more than 60%, and the water absorption rate is not less than 50%.

[0046] Further preferably, the present invention can design the amount of the reactor, the residence time of the flue gas in the reactor bed layer according to the flue gas flow rate, the flue gas velocity and the concentration of carbon oxides in the flue gas, and determine the structural dimensions of the catalytic reaction tower, the number of layers of the reactor bed layer, the height of the single layer and the layout, and the present invention does not limit the specific parameters. The catalytic reactor is loaded into the reaction tower, and the temperature is raised to 160-180°C. The flue gas flows into the tower body and enters the reactor bed layer through the smoke inlet pipe under the power of the induced draft fan. In the reactor, CO and CO2 in the flue gas are catalytically decomposed to generate C and O2. O2 is emptied through the flue under the action of the induced draft fan, and the C single substance is diffused into the air with the flue gas discharge, and after cooling, it aggregates into amorphous carbon single substance aggregates, which are generally in the state of quasi-graphene structure or amorphous structure aggregates of 16-32-64C protons at room temperature, falling into the soil or recycled into carbon black and other industrial raw materials.

[0047] It is further preferred that the reactor provided by the present invention can be recycled by physical grinding regeneration and chemical treatment regeneration during use. The general service life is more than 26,000 hours. The deactivated reactor can be 100% recycled and reused. The product of the present invention is environmentally friendly.

[0048] The beneficial effects of the present invention are at least as follows: after more than 20 years of technical research accumulation and thousands of experimental verifications, the present invention has successfully developed a low-temperature removal of sulfur oxides and nitrogen oxides and achieved ultra-low emission standards, and gradually achieved commercialization. At the same time, after continuous research, a new technology for low-temperature dry removal of CO2 and CO has been successfully developed. The innovative technology based on the catalytic synergy of multiple active substances in the porous structure to decompose and remove CO2 and CO at low temperatures has been verified through actual use to achieve a CO2 removal efficiency of more than 50% and a CO removal rate of more than 60% in industrial flue gas. The present invention is developed with the goal of being engineering-friendly, and the raw materials for production are easily available, the production process is simple and controllable, the operating cost is low, and the deactivated reactor can be recycled and reused. The promotion and use of the technology of the present invention can produce huge social and economic benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] To more clearly illustrate the technical solutions in the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0050] Figure 1 Schematic diagram of the reactor provided by the embodiment of the present invention.

[0051] Figure 2 Physical diagram of the reactor provided by the embodiment of the present invention.

[0052] Figure 3 Schematic cross-sectional view of the holes of the reactor provided by the embodiment of the present invention.

[0053] Figure 4 Schematic cross-sectional view of the holes of the reactor provided by the embodiment of the present invention.

[0054] Figure 5 Schematic partial view of the bed formed by stacking the reactors in the reaction tower provided by the embodiment of the present invention.

[0055] Figure 6 System for preparing the reactor provided by the embodiment of the present invention.

[0056] Figure 7 Schematic diagram of the decarbonization tower provided by the embodiment of the present invention.

[0057] Figure 8 Schematic diagram of the reaction system provided by the embodiment of the present invention.

[0058] In the figure, 1 - reactor; 2 - macropore; 3 - mesopore; 4 - clay kneader; 5 - granulator; 6 - sintering furnace; 7 - air cooler; 8 - reaction kettle; 9 - dryer; 10 - drying machine; 11 - mixer; 12 - ultrafine grinder; 13 - decarbonization tower; 14 - flue gas inlet pipe; 15 - flue gas outlet pipe; 16 - induced draft fan; 17 - chimney direct discharge bypass pipe. Detailed implementation manners

[0059] To make the objectives, technical solutions and advantages of the present invention clearer, the following will clearly and completely describe the technical solutions in the present invention. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art without creative efforts based on the embodiments in the present invention belong to the scope of protection of the present invention.

[0060] In the ranges disclosed in the present invention, the endpoints and any values of the ranges are not limited to the exact ranges or values. These ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed in the present invention.

[0061] For those not specifying specific technologies or conditions in the embodiments of the present invention, they shall be carried out according to the technologies or conditions described in the literature in this field or according to the product specifications. For those devices, instruments, reagents, etc. not indicating the manufacturer, they are all conventional products that can be purchased through regular channels.

[0062] An embodiment of the present invention provides a reactor for catalytically decomposing carbon oxides at low temperature, such as Figures 1 - 5 shown. The reactor 1 is a spherical reactor with a diameter greater than 15 mm. Macropores 2 and mesopores 3 are distributed on the surface and inside of the reactor 1. A catalyst for catalytically decomposing carbon oxides at low temperature is loaded in the macropores 2 and the mesopores 3. The specific surface area of the reactor is 1.00 - 2.00 m 2 / g, and the number of pores in the reactor is 1.00×10 11 -2.00×10 11 . The present invention designs and prepares a reactor for catalytically decomposing carbon oxides (CO2 and / or CO) at low temperature. A bed layer formed by multiple spherical reactors (the spherical reactors are closely stacked in the reaction tower and form a bed layer in the reaction tower) is used to treat carbon oxides through a dual-active catalytic system. In particular, by utilizing the synergistic effect of its binary porous structure (macropores, mesopores) and multi-layer (bed layer, macropores and mesopores) void volume structure, CO2 and CO in industrial flue gas are decomposed into harmless substances such as C and O2 at a low temperature of 160 - 180 °C. As a preferred embodiment, the diameter of the reactor is 20 - 40 mm. In a preferred embodiment, the mesoporous structure formed by loading the catalyst is an open pore structure and / or a cage group structure.

[0063] In a preferred embodiment, the water absorption rate of the reactor is ≥50%.

[0064] In a preferred embodiment, the void volume of the bed layer formed by stacking the spherical reactors is ≥60%. In the present invention, the reactor is a binary porous open structure, and the void volume is the multi-layer (bed layer, macropores and mesopores) void volume, that is, the void volume between the reactors in the bed layer and the void volume of the macropores and mesopores in the reactor.

[0065] In a preferred embodiment, the macropores contain mesopores; the number of mesopores in the macropores is 3.00×10 5 -5.00×10 5indivual.

[0066] In a preferred embodiment, the specific surface area of the mesopores is 100-2000nm 2 , such as 1700-2000nm 2 .

[0067] In the embodiment of the present invention, the number of active points generating dual active centers in the mesopores reaches 4.00×10 4 -5.00×10 4 A mesoporous reaction unit with fully inelastic collision and adsorption catalysis was established. This structure increases the number of pre-factors in the decomposition reaction of carbon oxides, reduces the bond energy, and reduces the decomposition activation energy to 120-150KJ / mol through dual-activity catalysis. It provides the kinetic conditions for the catalytic reaction to achieve the decomposition and removal of CO2 and CO at 160-180℃.

[0068] In a further preferred embodiment, the catalyst for the low-temperature catalytic decomposition of carbon oxides is a dual-activity catalytic system for the low-temperature catalytic decomposition of CO2 and CO. In the present invention, the catalyst for the low-temperature catalytic decomposition of carbon oxides / the dual-activity catalytic system for the low-temperature catalytic decomposition of CO2 and CO can adopt catalytic materials known in the art (dual-activity catalytic system for the low-temperature catalytic decomposition of CO2 and CO). The dual activity is a single-activity catalytic system for the conversion of carbon dioxide to carbon monoxide, and a single-activity catalytic system for the low-temperature catalytic decomposition of carbon monoxide, thereby realizing the decomposition of carbon dioxide into carbon monoxide, and the low-temperature catalytic decomposition of carbon monoxide into carbon element and oxygen.

[0069] In a further preferred embodiment, the shape of the bed layer includes a cylinder, a cube, a cuboid or an irregular body.

[0070] As a preferred embodiment, Figure 6 As shown, the preparation device of the reactor 1 includes a dryer 10, an ultrafine grinder 12, a mixer 11, a mud kneading machine 4, a granulator 5, a sintering kiln 6, an air cooler 7, a reactor 8 and a dryer 9; the mixer 11 is connected to the mud kneading machine 4, the mud kneading machine 4 is connected to the granulator 5, the granulator 5 is connected to the dryer 10, the dryer 10 is connected to the sintering kiln 6, the sintering kiln 6 is connected to the reactor 8, the reactor 8 is connected to the dryer 9, the air cooler 7 is connected to the sintering kiln 6, and the ultrafine grinder 12 is connected to the mixer 11.

[0071] In a further preferred embodiment, the mixer 11 is a twin-screw mixer; the clay kneading machine 4 is a clay kneading machine for ceramic production; the granulator 5 is an extruder; and the sintering kiln 6 is an electric high-temperature muffle furnace or a gas furnace.

[0072] An embodiment of the present invention further provides a reaction system for catalytically decomposing carbon oxides at low temperature ( Figure 7 and Figure 8 ), which includes a decarbonization tower 13, and a flue gas inlet pipe 14 and a flue gas outlet pipe 15 connected to both ends of the decarbonization tower 13. At least one layer of bed for catalytically decomposing carbon oxides at low temperature is provided in the decarbonization tower 13, such as two layers, three layers, four layers, etc. The bed is formed by tightly stacking a plurality of the reactors 1. The reactors (multiple layers of beds) placed in the decarbonization tower 13 perform catalytic decomposition at low temperature. The gas to be treated can enter through the flue gas inlet pipe 14, and better pass through the reactors for catalytic decomposition, and is discharged through the flue gas outlet pipe 15.

[0073] As a preferred embodiment, the system further includes a draft fan 16, a chimney direct discharge bypass pipe 17 and a stop valve; the draft fan 16 is connected to the flue gas outlet pipe 15, one end of the chimney direct discharge bypass pipe 17 is connected to the flue gas outlet pipe 15, the other end of the chimney direct discharge bypass pipe 17 is connected to the flue gas inlet pipe 14, the stop valve is provided on the flue gas inlet pipe 14, the flue gas outlet pipe 15 and the chimney direct discharge bypass pipe 17, and the flue gas outlet pipe 15 is connected to the chimney.

[0074] Based on the above embodiments, the following will be further described in combination with specific embodiments.

[0075] Embodiment 1 The reactor for catalytically decomposing CO2 and CO at low temperature provided in this embodiment.

[0076] By weight, the matrix raw material composition of the reactor includes: 40 parts of fly ash, 10 parts of dry soil, 5 parts of bentonite, 10 parts of binder, 10 parts of pore former, 15 parts of main active precursor, 5 parts of co-active precursor, and 5 parts of adsorbent. The main active precursor is manganese oxide, cerium oxide and copper oxide with a molar ratio of 6:4:1. The co-active precursor is Fe2SO3, NiO, Nb2O5, MoO, TiO2 and ZrO with a molar ratio of 8:2:2:3:1:1. The binder is CMC and flour with a mass ratio of 1:1. The pore former is starch and epoxy resin with a mass ratio of 1:1. The adsorbent is nickel oxide and ferrous sulfate with a mass ratio of 2:1. The fly ash is the fly ash generated after the combustion of a chain grate furnace with bituminous coal as the main fuel. The components in the fly ash are in weight ratio: SiO2: 53%, Al2O3: 31%, MgO: 3%, CaO: 2%, K2O: 3%, Fe2O3: 5%, Na2O 1%, and the balance is inevitable impurities.

[0077] The raw materials of the reactor also include a nitric acid solution with a volume ratio of 1:1 to the reactor matrix and an acid leaching solution with a volume ratio of 1:1 to the reactor matrix. The concentration of the nitric acid solution is 30%. The acid leaching solution is a nitric acid solution of the main active substance and the co-active substance. Among them, the main active substance is copper nitrate, cerium nitrate, and manganese acetate (copper-manganese-cerium composite acidic catalyst) with a molar ratio of Mn:Ce:Cu of 6:4:1. The co-active substance is ferrous sulfate, nickel nitrate, niobium nitrate, and cobalt nitrate with a molar ratio of 1:1:2:1. The weight ratio of the main active substance and the co-active substance in the acid leaching solution is 25%, and the mass ratio of the main active substance and the co-active substance is 10:1, and the nitric acid concentration is 30%.

[0078] The preparation method of the low-temperature catalytic decomposition CO2 and CO reactor provided in this embodiment is as follows: The materials that are insoluble in water and have a low content (main active precursor, co-active precursor, adsorbent) are calcined in an electric furnace at 325 - 340 °C for 4 - 5 h, and then pulverized into ultrafine meshes. The remaining materials (except for the acid leaching solution and nitric acid) are mixed by a mixer and mixed with the pulverized materials under the action of water medium. Through the mixer, they are kneaded at room temperature for 3 - 4 h to make each component fully mixed and uniform. The materials are sealed and fermented for 48 h. They are formed into spherical embryos with a diameter of 25 - 27 mm in a granulator. They are naturally air-dried at a temperature of 35 - 50 °C for 48 h (or dried at 115 - 120 °C for 3 - 4 h). The dried embryos are placed in a muffle furnace (or in a gas furnace) and calcined at 860 - 890 °C for 7 - 8 h to make the reactor matrix.

[0079] The surface of the matrix is polished. In order to increase the specific surface area of the matrix and remove the scaling layer generated on the surface of the reactor matrix during calcination, it is soaked in a nitric acid solution with a concentration of 30% (weight ratio), and the reactor matrix is soaked at a volume ratio of 1:1 at 30 - 45 °C for 3 - 5 h. After drying, it is dried at 220 - 240 °C for 3 - 4 h.

[0080] Load the main active substance and the co-active substance. Mix the main active substance and the co-active substance with nitric acid to form an acid leaching solution. Soak them at an equal volume ratio at 25 - 40 °C for 3 - 5 h, dry them at 120 - 150 °C for 8 - 10 h, and then place them in an electric furnace and calcine them at 380 - 400 °C for 6 - 8 h to make a low-temperature catalytic decomposition CO2 and CO reactor, and then vacuum package it.

[0081] In actual use, the structure of the reaction system includes a flue gas inlet pipe, a decarbonization tower, a flue gas outlet pipe, a draft fan, a chimney direct discharge bypass pipe, and a stop valve. Among them: the flue gas inlet pipe is connected to the decarbonization tower through a stop valve, the lower end (or side end) of the decarbonization tower is connected to the flue gas outlet pipe, the flue gas outlet pipe is connected to the draft fan through a stop valve, and the draft fan is connected to the chimney direct discharge bypass pipe. The decarbonization tower is filled with a cylindrical bed layer formed by stacking multiple reactors.

[0082] Based on the flue gas flow rate and the concentration of carbon oxides, the dosage of the catalyst, the residence time of the flue gas, the flue gas velocity, etc. are calculated, and the diameter of the catalytic tower, the number of layers of the reactor bed, the single-layer height and the layout are determined. This embodiment is actually used in the flue gas treatment such as decarbonization in Chengde Zhongluan Coal Chemical Industry Co., Ltd. The flue gas flow rate is 20,000 cubic meters per hour, and the carbon dioxide concentration is 12.30%. The designed dosage of the low-temperature catalytic decomposition carbon oxide reactor is 4.0 cubic meters, the flue gas velocity is 6 m / s, and the layout is two layers. The catalytic reactor is placed in the reaction tower, and the temperature is raised to make the temperature of the reactor and the tower rise to 160 - 180 °C. The flue gas flows into the tower through the inlet flue under the action of the induced draft fan and enters the reactor. In the reactor, the catalytic decomposition reaction of CO and CO2 in the waste flue gas occurs to generate C and O2. O2 is discharged through the flue under the action of the induced draft fan, while the C single substance diffuses into the air with the flue gas emissions. After cooling, it aggregates into an amorphous structure carbon single substance aggregate, and generally its state at normal temperature is an 8 - 16 - 32 - 64C proton quasi-graphene structure or an amorphous structure aggregate, which falls into the soil or is recycled to make carbon black.

[0083] The low-temperature catalytic decomposition CO2 and CO reactor made in this embodiment, the reactor is a macroporous and mesoporous binary spherical structure, its sphere diameter is 25 - 26 mm, the specific surface area is 1.20 - 2.00 m 2 / g, the bulk specific gravity is 935 - 950 kg per cubic meter, the number of pores of each reactor is 1.20×10 11 -2.00×10 11 pieces, the macropore diameter is 1600 - 1900 nm, the number of mesopores formed in the macropores after loading the catalyst is 3.00×10 5 -4.00×10 5 , the mesopore diameter is 20 - 30 nm, the multi-layer void volume is 65% - 75%, and the water absorption rate is 58% - 60%. In the actual use of Chengde Zhongluan Coal Chemical Industry Co., Ltd., after testing, the carbon monoxide removal rate reaches 68% at 160 - 180 °C, and the carbon dioxide removal rate is 62%.

[0084] Example 2 Same as Example 1, the difference is that the following raw materials of the reactor are changed to: 40 parts of fly ash, 10 parts of dry soil, 5 parts of bentonite, 5 parts of binder, 15 parts of pore former, 15 parts of main active precursor, 5 parts of co-active precursor, and 10 parts of adsorbent. Main active substances: copper nitrate, cerium nitrate, manganese acetate according to the molar ratio of Mn:Ce:Cu = 6:3:2 (copper-manganese-cerium composite acidic catalyst), and the co-active substances are ferrous sulfide, nickel nitrate, niobium nitrate and titanium nitrate with a molar ratio of 2:1:1:1.

[0085] In the use and detection of the low-temperature catalytic decomposition CO2 and CO reactor made in this embodiment, the carbon monoxide removal rate reaches 52% at 160 - 180 °C, and the carbon dioxide removal rate is 45%.

[0086] Example 3 Same as Example 1, except that the following raw materials of the reactor are changed to: 40 parts of fly ash, 10 parts of dry soil, 10 parts of fluorite powder, 10 parts of binder, 10 parts of pore former, 10 parts of main active precursor, and 5 parts of auxiliary active precursor.

[0087] In this example, the binder is CMC and flour with a mass ratio of 2:1. The pore former is pulverized coal and epoxy resin with a mass ratio of 1:1. The adsorbent is nickel oxide, magnesium oxide, and iron oxide with a mass ratio of 1:1:3.

[0088] The low-temperature catalytic decomposition CO2 and CO reactor made in this example has a carbon monoxide removal rate of 60% and a carbon dioxide removal rate of 35% at 160 - 180 °C during actual use in the laboratory tower.

[0089] Example 4 When the other conditions in Example 1 remain unchanged and the catalytic reaction temperature is increased to 190 - 200 °C, the carbon monoxide removal rate of the low-temperature decomposition CO2 and CO reactor in this example reaches 80%, and the carbon dioxide removal rate reaches 75%.

[0090] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present invention and are not intended to limit them; although the present invention has been described in detail with reference to the foregoing examples, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing examples, or perform equivalent replacements for some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A reactor for catalytically decomposing carbon oxides at low temperature, characterized in that, The reactor is a spherical reactor with a diameter greater than 15 mm. Macropores and mesopores are distributed on the surface and inside of the reactor. The macropores and mesopores are loaded with a catalyst. The specific surface area of the reactor is 1.00 - 2.00 m 2 / g, and the number of pores in the reactor is 1.00×10 11 -2.00×10 11 .

2. The reactor for catalytically decomposing carbon oxides at low temperature according to claim 1, characterized in that, The void volume of the packed bed of the spherical reactors ≥ 60%. and / or, the diameter of the reactor is 20 - 40 mm; and / or, the mesoporous structure formed by the supported catalyst is an open pore structure and / or a cage group structure; and / or, the water absorption rate of the reactor ≥ 50%; And / or, the macropores contain mesopores, and the number of mesopores in the macropores is 3.00×10 5 -4.00×10 5 pieces; and / or, the specific surface area of the mesopores is 1000-2000 nm 2 .

3. The reactor for catalytically decomposing carbon oxides at low temperature according to claim 1 or 2, characterized in that, The reactor comprises the following raw materials in parts by weight: 40 - 50 parts of fly ash, 5 - 10 parts of dry subsoil, 5 - 15 parts of bentonite, 15 - 20 parts of main active precursor, 5 - 10 parts of co - active precursor, 5 - 15 parts of binder, 5 - 20 parts of pore former, 5 - 10 parts of adsorbent.

4. The reactor for catalytically decomposing carbon oxides at low temperature according to claim 3, characterized in that, The main active precursor is manganese oxide, cerium oxide and copper oxide; preferably, the molar ratio of manganese oxide, cerium oxide and copper oxide is 4 - 7:3 - 5:0.5 - 2; and / or, the co - active precursor is selected from one or more of Fe2SO3, NiO, Nb2O5, MoO, TiO2 and ZrO; preferably, the molar ratio of Fe2SO3, NiO, Nb2O5, MoO, TiO2 and ZrO is 2 - 10:1 - 5:1 - 5:1 - 5:0.5 - 2:0.5 - 2.

5. The reactor for catalytically decomposing carbon oxides at low temperature according to claim 3 or 4, characterized in that, The fly ash is the fly ash produced after the combustion of a chain furnace with bituminous coal as the main fuel; the fly ash comprises by weight: SiO2: 40% - 60%, Al2O3: 25% - 45%, MgO: 1% - 5%, CaO: 1% - 4%, K2O: 1% - 3%, Fe2O3: 0.1% - 5%, Na2O 1% - 3%. and / or, the binder is CMC and / or flour; and / or, the pore former is selected from one or more of starch, pulverized coal and epoxy resin; and / or, the adsorbent comprises one or more of nickel oxide, magnesium oxide, niobium oxide, iron oxide and titanium oxide; Preferably, the raw materials of the reactor further comprise acid leaching solution and / or nitric acid solution. The concentration of the nitric acid solution is 25% - 30%; the acid leaching solution is a nitric acid solution of main active substances and co - active substances, the main active substances are selected from one or more of copper nitrate, cerium nitrate and manganese acetate, and the co - active substances are selected from one or more of ferrous sulfate, nickel nitrate, niobium nitrate, cobalt nitrate and titanium nitrate.

6. A method for preparing a reactor for catalytically decomposing carbon oxides at low temperature according to any one of claims 1-5, characterized in that, Comprising: 1) Matrix preparation: Mix the raw materials of the reactor, then let the mixture sit and ferment, then granulate and dry, and calcine the dried embryo to obtain the reactor matrix; 2) Carrier casting: Immerse the reactor matrix in nitric acid solution to obtain the reactor matrix after carrier casting; 3) Loading of main active substances and co - active substances: Immerse the reactor matrix after carrier casting in an acid leaching solution containing main active substances and co - active substances for equal - volume immersion, dry and then calcine.

7. The method for preparing a reactor for catalytically decomposing carbon oxides at low temperature according to claim 6, characterized in that, In step 1), the diameter of the spherical embryo after granulation is 20 - 40 mm; the drying is natural air drying at 30 - 50 °C for 45 - 50 h, or drying at 100 - 120 °C for 2 - 5 h; the dried embryo is calcined at 800 - 980 °C for 5 - 20 h.

8. The method for preparing a reactor for catalytically decomposing carbon oxides at low temperature according to claim 6 or 7, characterized in that, In step 2), the concentration of the nitric acid solution is 20%-40%, the soaking temperature is 30-50°C, soak for 3-6 h in equal volume and then dry at 100-200°C for 3-5 h; And / or, in step 3), soak the reactor matrix after pelletizing the carrier in equal volume at 20-40°C for 3-6 h, dry at 100-300°C for 8-10 h, and calcine at 300-500°C for 5-8 h.

9. The method for preparing a reactor for catalytically decomposing carbon oxides at low temperature according to any one of claims 6-8, characterized in that, The preparation device of the reactor includes a dryer, an ultrafine grinder, a mixer, a clay kneader, a granulator, a sintering furnace, an air cooler, a reaction kettle and a dryer; the mixer is connected to the clay kneader, the clay kneader is connected to the granulator, the granulator is connected to the dryer, the dryer is connected to the sintering furnace, the sintering furnace is connected to the reaction kettle, the reaction kettle is connected to the dryer, the air cooler is connected to the sintering furnace, and the ultrafine grinder is connected to the mixer; preferably, the mixer is a twin-screw mixer; the clay kneader is a clay kneader for ceramic production; the granulator is an extruder; the sintering furnace is an electric high-temperature muffle furnace or a gas furnace.

10. An application system for catalytically decomposing carbon oxides at low temperature, characterized in that, It includes a decarbonization tower, and a flue gas inlet pipe and a flue gas outlet pipe connected to both ends of the decarbonization tower. The reactor for low-temperature catalytic decomposition of carbon oxides according to any one of claims 1-5 is provided in the decarbonization tower; preferably, the application system further includes a draft fan, a chimney direct discharge bypass pipe and a stop valve; the draft fan is connected to the outlet pipe, and also includes a draft fan, a chimney direct discharge bypass pipe and a stop valve; the draft fan is connected to the outlet pipe, one end of the chimney direct discharge bypass pipe is connected to the outlet pipe, the other end of the chimney direct discharge bypass pipe is connected to the inlet pipe, and the stop valve is provided on the inlet pipe, the outlet pipe and the chimney direct discharge bypass pipe.

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