Ceramic filler for catalytic desorption of carbon dioxide and preparation method thereof

Abstract

The invention relates to a ceramic filler for catalytic desorption of carbon dioxide and a preparation method thereof, and the ceramic filler comprises, based on the total weight of the ceramic filler, 70-95 wt% of a matrix material, 0.8-20 wt% of an active component loaded on the matrix material, and 0.3-15 wt% of an organic dopant; the matrix material comprises one or more of porous materials; the active component is selected from one or more of metal oxides and non-metal oxides; wherein the metal is selected from one or more of IIIA group elements, IVB group elements and VIII group elements, and the nonmetal is selected from one or more of IIIA group elements and IVA group elements. In the thermal desorption process of the ceramic filler, reaction barriers can be reduced, the reaction rate can be increased, and the desorption temperature of an organic amine absorbent can be reduced.

Description

Technical Field

[0001] The present disclosure relates to the field of carbon dioxide capture, and in particular, to a ceramic filler for catalytically desorbing carbon dioxide and a preparation method thereof. Background Art

[0002] The current low-concentration carbon dioxide capture technologies mainly include chemical absorption, physical absorption, physical adsorption, membrane separation, and cryogenic separation. The chemical absorption method is currently basically mature and is in the industrial demonstration stage. It uses the chemical reaction between chemical reagents and CO2 to separate CO2 from flue gas. Commonly used chemical agents include monoethanolamine (MEA), diethanolamine (DEA), methyldiethanolamine (MDEA), composite amines, and sterically hindered amines. Conventional rich liquid desorption methods include thermal desorption, membrane desorption, and decompression desorption. At present, the industrial demonstration device of chemical absorption method uses thermal desorption. Its principle is that the rich liquid enters the desorption device and is heated to above 100°C, so that CO2 is fully desorbed. The main equipment is the desorption tower, and the packing is installed in the desorption tower to increase the contact area. Conventional packed towers use structured packing and random packing. The general packing requires an increase in the heat and mass transfer area. The packing has a large flux and low resistance, a high porosity, a large specific surface area, and good wettability on the surface.

[0003] However, the main problems faced by the existing technology include high heat consumption during the desorption and regeneration process, which in turn affects large-scale promotion and application. Summary of the invention

[0004] The purpose of the present disclosure is to provide a ceramic filler for catalytic desorption of carbon dioxide and a preparation method thereof. During the desorption process, the ceramic filler can reduce the reaction barrier, increase the reaction rate, and effectively reduce the heat required for desorption.

[0005] In order to achieve the above-mentioned object, the first aspect of the present disclosure provides a ceramic filler for catalytic desorption of carbon dioxide, wherein the ceramic filler comprises 70 to 95 weight % of a matrix material, 0.8 to 20 weight % of an active ingredient loaded on the matrix material, and 0.3 to 15 weight % of an organic dopant, based on the total weight of the ceramic filler; The matrix material comprises one or more porous materials; the active ingredient is selected from one or more metal oxides and non-metal oxides; wherein the metal is selected from one or more elements of Group IIIA, Group IVB and Group VIII, and the non-metal is selected from one or more elements of Group IIIA and Group IVA.

[0006] Optionally, the ceramic filler comprises 90-95 wt % of a matrix material, 0.8-5 wt % of an active ingredient and 0.3-5 wt % of an organic dopant loaded on the matrix, based on the total weight of the ceramic filler; Optionally, the weight ratio of the matrix material to the active ingredient is 9-6:1, preferably 8-7:1.

[0007] Optionally, the matrix material is selected from one or more of titanium dioxide and molecular sieves, and the molecular sieve is selected from one or more of ZSM molecular sieves, Y molecular sieves and HZ molecular sieves; preferably titanium dioxide; preferably, the matrix material has an average particle size of 0.1nm to 50nm, an average pore size of 1nm to 20nm, and a BET specific surface area of ​​1 to 1000m 2 / g, pore volume 0.01~10cm 3 / g; Optionally, the metal oxide is selected from one or more of Al2O3, ZrO2, Fe2O3 and Fe3O4, and the non-metal oxide is selected from one or more of B2O3 and SiO2; preferably B2O3; the pore size of the non-metal oxide is 2-50nm, preferably 1nm-20nm; the average particle size of the non-metal oxide is 1-20nm, preferably 5-10nm; Optionally, the organic dopant includes piperazine and / or pyridine.

[0008] Optionally, the ceramic filler is formed as a structured filler or a random filler; the filler form of the structured filler includes one or more of a plate type, a corrugated plate type and a honeycomb type; the filler form of the random filler includes one or more of a triple Y ring, a Raschig ring, a cross partition ring, a Pall ring, a rectangular saddle ring, an iso-saddle ring, a conjugate ring and a flat ring.

[0009] A second aspect of the present disclosure provides a method for preparing a ceramic filler for catalytically desorbing carbon dioxide, comprising the following steps: S1, contacting the matrix material with the active component in the organic dopant to load the active component and the organic dopant to obtain a first product; S2, subjecting the first product to molding, curing and drying processes; The matrix material comprises one or more porous materials; the active ingredient comprises one or more metal oxides and non-metal oxides; the metal is selected from Group IIIA, Group IVB and Group VIII, and the non-metal is selected from Group IIIA and Group IVA.

[0010] Optionally, the organic dopant comprises piperazine and / or pyridine; The weight ratio of the organic dopant to the active ingredient is 0.01-3:1, preferably 0.1-1:1.

[0011] Optionally, in step S1, the matrix material and the active ingredient are added in a weight ratio of 9 to 6:1, preferably 8 to 7:1; The matrix material is selected from one or more of titanium dioxide and molecular sieves, and the molecular sieve is selected from one or more of ZSM molecular sieves, Y molecular sieves and HZ molecular sieves; preferably titanium dioxide; Optionally, the metal oxide is selected from one or more of Al2O3, ZrO2, Fe2O3 and Fe3O4; the non-metal oxide is selected from one or more of B2O3 and SiO2; preferably B2O3.

[0012] Optionally, the contact conditions in step S1 include a contact temperature of 0 to 50° C., preferably 10 to 30° C.; a contact time of 4 to 24 h, preferably 6 to 16 h; and a stirring rate of 100 to 600 rpm, preferably 200 to 400 rpm.

[0013] Optionally, in step S2, the drying treatment conditions include a temperature of 100-400° C., preferably 110-200° C., and a time of 6-40 hours, preferably 8-18 hours; The curing treatment conditions include a temperature of 0 to 60° C., preferably 15 to 30° C., and a time of 3 to 24 hours, preferably 6 to 16 hours.

[0014] A third aspect of the present disclosure provides a ceramic filler prepared using the method described in the second aspect of the present disclosure.

[0015] Through the above technical scheme, the present disclosure provides a ceramic filler for catalytic desorption of carbon dioxide and a preparation method. The ceramic filler disclosed in the present disclosure includes a ceramic filler matrix, an active ingredient and an organic dopant. During the thermal desorption process, the reaction barrier can be reduced, the reaction rate can be increased, and less heat is required. The desorption temperature of the organic amine absorbent can be reduced from 105~120°C in the conventional MEA desorption method to 75~98°C. The desorption temperature is significantly reduced. The ceramic filler disclosed in the present disclosure can reduce the regeneration energy consumption by 10~30%.

[0016] Other features and advantages of the present disclosure will be described in detail in the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The accompanying drawings are used to provide a further understanding of the present disclosure and constitute a part of the specification. Together with the following specific embodiments, they are used to explain the present disclosure but do not constitute a limitation of the present disclosure. In the accompanying drawings: Figure 1 It is a schematic structural diagram of a desorption tower for catalytic desorption of carbon dioxide disclosed in the present invention. Figure 2 It is a schematic diagram of the structure of a system for catalytic desorption of carbon dioxide disclosed in the present invention.

[0018] Description of Reference Numerals 1: Wire mesh demister; 2: Liquid distributor; 3: Packing pressure ring; 4: Packing unit; 5: Filter screen; 7: Packing support; 8: Reaction stirring device; 9: Tubular distributor; A: Graded flow inlet; a: Rich liquid inlet; b: Amine liquid outlet; c: Lean liquid outlet; d: Regeneration gas outlet; e: Amine steam inlet; f: Liquid replenishment port; g: Pressure relief port; h: Amine steam port; i: Flash steam inlet; k: Drain port; l: Manhole; m: Automatic liquid level gauge interface; n: On-site liquid level gauge interface; o: Boiler interface; p: Temperature detection port; q: Pressure detection port; s: Sampling port; T: Thermal siphon return liquid port; U: Flue gas test port; 11: Desorption tower; 12: Boiler; 13: Desorption tower liquid inlet; 14: Catalyst inlet; 15: Catalyst outlet; 16: External steam inlet; 17: Condensate outlet; 18: Boiler drain port. DETAILED DESCRIPTION

[0019] The specific implementation of the present disclosure is described in detail below in conjunction with the accompanying drawings. It should be understood that the specific implementation described herein is only used to illustrate and explain the present disclosure, and is not used to limit the present disclosure.

[0020] In a first aspect, the present disclosure provides a ceramic filler for catalytically desorbing carbon dioxide, wherein the ceramic filler comprises, based on the total weight of the ceramic filler, 70 to 95 wt % of a matrix material, 0.8 to 20 wt % of an active ingredient loaded on the matrix material, and 0.3 to 15 wt % of an organic dopant; The matrix material comprises one or more porous materials; the active ingredient is selected from one or more metal oxides and non-metal oxides; wherein the metal is selected from Group IIIA, Group IVB and Group VIII, and the non-metal is selected from Group IIIA and Group IVA.

[0021] According to one embodiment of the present disclosure, the ceramic filler includes 90% to 95% by weight of a matrix material, 0.8% to 5% by weight of an active ingredient and 0.3 to 5% by weight of an organic dopant loaded on the matrix, based on the total weight of the ceramic filler. In a further embodiment, the weight ratio of the matrix material to the active ingredient is 9 to 6:1, preferably 8 to 7:1. The above embodiment is conducive to obtaining a suitable ceramic filler, thereby reducing the reaction barrier, increasing the reaction rate, requiring less heat, and reducing the desorption temperature of the organic amine absorbent.

[0022] According to one embodiment of the present disclosure, the matrix material is selected from one or more of titanium dioxide and molecular sieves, and the molecular sieve is selected from one or more of ZSM molecular sieves, Y molecular sieves and HZ molecular sieves; preferably titanium dioxide. In a further embodiment, the average particle size of the matrix material is 0.1-50 nm, preferably 1 nm-20 nm; the average pore size is 1-20 nm, preferably 5-15 nm; the BET specific surface area is 1-1000 m 2 / g, preferably 10~100m 2 / g; pore volume is 0.01~10 cm 3 / g, preferably 0.05~3cm 3 The above implementation is conducive to obtaining a suitable ceramic filler, thereby reducing the reaction barrier, increasing the reaction rate, requiring less heat, and reducing the desorption temperature of the organic amine absorbent.

[0023] According to one embodiment of the present disclosure, the metal oxide is selected from one or more of Al2O3, ZrO2, Fe2O3 and Fe3O4, and the non-metal oxide is selected from one or more of B2O3 and SiO2; preferably B2O3. In a further embodiment, the pore size of SiO2 is 2~50nm, preferably 5~20nm; the average particle size of SiO2 is 0.1~50nm, preferably 1~30nm; the purity of SiO2 can be 99.9%~99.999%; the pore size of B2O3 is 10~15nm. The pore size of SiO2 or B2O3 is in a suitable range, which is conducive to increasing the catalytic contact area and obtaining ceramic filler particles with excellent performance. In the above preferred embodiment, it is conducive to obtaining ceramic filler particles with excellent performance and further reducing the desorption temperature and energy consumption of the organic amine absorbent.

[0024] According to one embodiment of the present disclosure, the organic dopant includes piperazine and / or pyridine, preferably piperazine.

[0025] According to one embodiment of the present disclosure, the ceramic filler is formed as a structured filler or a random filler; the filler form of the structured filler includes one or more of a plate structured filler, a corrugated plate structured filler and a honeycomb structured filler; the filler form of the random filler includes one or more of a triple Y ring, a Raschig ring, a cross partition ring, a ball ring, a rectangular saddle ring, an iso-saddle ring, a conjugate ring and a flat ring.

[0026] The above implementation is conducive to obtaining a suitable ceramic filler, thereby reducing the reaction barrier, increasing the reaction rate, requiring less heat, and reducing the desorption temperature of the organic amine absorbent. In one implementation, the average particle size of the ceramic filler particles is 10nm~10μm, preferably 100nm~500nm.

[0027] A second aspect of the present disclosure provides a method for preparing a ceramic filler for catalytically desorbing carbon dioxide, comprising the following steps: S1, contacting the matrix material with the active component in the organic dopant to load the active component and the organic dopant to obtain a first product; S2, subjecting the first product to molding, curing and drying processes; The matrix material comprises one or more porous materials; the active ingredient comprises one or more metal oxides and non-metal oxides; the metal is selected from one or more of Group IIIA, Group IVB and Group VIII, and the non-metal is selected from one or more of Group IIIA and Group IVA.

[0028] According to an embodiment of the present disclosure, the organic dopant includes piperazine and / or pyridine, preferably piperazine; the weight ratio of the organic dopant to the active ingredient is 0.01-3:1, preferably 0.1-1:1. The above embodiment is conducive to obtaining a suitable ceramic filler, thereby reducing the reaction barrier, increasing the reaction rate, requiring less heat, and reducing the desorption temperature of the organic amine absorbent.

[0029] According to one embodiment of the present disclosure, the matrix material is selected from one or more of titanium dioxide and molecular sieves, and the molecular sieve is selected from one or more of ZSM molecular sieves, Y molecular sieves and HZ molecular sieves; preferably titanium dioxide.

[0030] According to an embodiment of the present disclosure, the metal oxide is selected from one or more of Al2O3, ZrO2, Fe2O3 and Fe3O4; the non-metal oxide is selected from one or more of B2O3 and SiO2; preferably B2O3. The above embodiment is conducive to obtaining a suitable ceramic filler, thereby reducing the reaction barrier, increasing the reaction rate, requiring less heat, and reducing the desorption temperature of the organic amine absorbent.

[0031] According to an embodiment of the present disclosure, the contact conditions in step S1 include a contact temperature of 0 to 50°C, preferably 10 to 30°C; a contact time of 4 to 24 hours, preferably 6 to 16 hours; and a stirring rate of 100 to 600 rpm, preferably 200 to 400 rpm. The above embodiment is conducive to obtaining a suitable ceramic filler, thereby reducing the reaction barrier, increasing the reaction rate, requiring less heat, and reducing the desorption temperature of the organic amine absorbent.

[0032] According to an embodiment of the present disclosure, in step S2, the drying treatment conditions include a temperature of 100-400°C, preferably 110-200°C; a time of 6-40 hours, preferably 10-18 hours; the curing treatment conditions include a temperature of 0-60°C, preferably 15-30°C; a time of 3-24 hours, preferably 6-16 hours. The above embodiment is conducive to obtaining a suitable ceramic filler, thereby reducing the reaction barrier, increasing the reaction rate, requiring less heat, and reducing the desorption temperature of the organic amine absorbent.

[0033] A third aspect of the present disclosure provides a ceramic filler prepared using the method described in the second aspect of the present disclosure.

[0034] According to one embodiment of the present disclosure, Figure 1 The desorption tower shown in the figure comprises a packing layer, wherein the packing layer comprises the ceramic packing described in the first aspect of the present disclosure and / or the third aspect of the present disclosure; the desorption tower comprises a rich liquid inlet a, an amine liquid outlet b, an amine steam inlet e, a packing unit 4, an amine liquid reaction chamber and a reaction stirring device 8; the reaction stirring device 8 is arranged in the amine liquid reaction chamber, and is used for stirring during the contact reaction between the amine liquid and the packing.

[0035] The desorption tower disclosed in the present invention includes a reaction stirring device, which is conducive to the full contact and reaction between the catalyst and filler in the amine liquid reaction chamber and the CO2-rich amine liquid in the tower, and further improves the desorption effect of desorbing carbon dioxide.

[0036] According to one embodiment of the present disclosure, Figure 1 As shown, the packing unit 4 includes a plurality of packing layers arranged at intervals; the distance between two adjacent packing layers is 1-6 m. In a further embodiment, the packing layer includes a first packing layer, a second packing layer and a third packing layer; a packing pressing ring 3 is arranged on the top of each packing layer, a packing support 7 is arranged on the bottom, and packing is filled in the packing layer.

[0037] According to one embodiment of the present disclosure, Figure 1 As shown, the desorption tower includes a liquid distributor 2 and a filter 5; the liquid distributor 2 is arranged on the top of the packing unit 4; the filter 5 is arranged on the upper part of the liquid distributor 2. In a further embodiment, the liquid distributor 2 is a trough-disc type liquid distributor. In one embodiment, the pore size of the filter 5 can be selected according to the particle size of the catalyst and the packing particles. The above-mentioned embodiment is conducive to the uniform distribution of the CO2-rich amine liquid on the packing, while preventing the packing in the packing layer from leaking into other packing layers, ensuring sufficient contact between the CO2-rich amine liquid and the packing in each packing layer.

[0038] According to one embodiment of the present disclosure, Figure 1As shown, the reaction stirring device 8 includes a stirring paddle, the desorption tower is provided with a stirring port, the stirring paddle includes a stirring rod and a stirring blade connected, the stirring rod extends from the stirring port of the desorption tower from the outside of the tower into the inside of the tower so that the stirring blade is located in the amine liquid reaction chamber of the desorption tower; a part of the stirring rod is located outside the desorption tower to connect to the motor. In a further embodiment, the height of the amine liquid reaction chamber is 0.5~5m, the stirring port is provided on the tower wall of the amine liquid reaction chamber, and the height distance between the stirring port and the bottom of the lower head of the desorption tower is 0.5~2m.

[0039] According to one embodiment of the present disclosure, Figure 1 As shown, the desorption tower includes a lean liquid outlet c, which is arranged below the amine liquid reaction chamber. The height distance between the lean liquid outlet c and the bottom of the lower head of the desorption tower is 0.1~1m.

[0040] According to one embodiment of the present disclosure, Figure 1 As shown, the amine liquid reaction chamber includes a thermal siphon liquid return port T, a flash steam inlet i, a boiler interface o and an amine steam port h.

[0041] In a specific implementation manner, Figure 1 As shown, the amine liquid outlet b, the thermosiphon liquid return port T and the amine steam inlet e are arranged longitudinally in sequence on the tower wall of the amine liquid reaction chamber; the flash steam inlet i and the amine steam port h are arranged in the same horizontal direction; the amine liquid outlet b is 0.1~2m higher than the amine steam inlet e; the thermosiphon liquid return port T is 0.2~2m higher than the amine steam inlet e; the boiler interface o is arranged at the lower part of the flash steam inlet i, and the distance from the flash steam inlet i is 0.5~2m. The above implementation is conducive to improving the desorption effect of desorbing carbon dioxide and further reducing the desorption temperature of the organic amine absorbent.

[0042] According to one embodiment of the present disclosure, the desorption tower is provided with a stirring port, and the stirring port is arranged below the amine steam port h, with a spacing of 0.3~1m.

[0043] According to one embodiment of the present disclosure, Figure 1 As shown, the desorption tower also includes a wire mesh demister 1, a tubular distributor 9, a graded flow inlet A, a regeneration gas outlet d, a liquid replenishment port f, a pressure relief port g, a sewage outlet k, a temperature detection port p, a pressure detection port q, a sampling port s and a flue gas test port U. The wire mesh demister 1 is arranged at the top of the desorption tower to reduce the volatilization of the CO2-rich amine liquid and the CO2-rich amine liquid carried by the regeneration gas when the CO2 is discharged, thereby reducing the loss of the CO2-rich amine liquid. The tubular distributor 9 is arranged above the packing unit 4, which is conducive to the uniform distribution of the CO2-rich amine liquid on the packing.

[0044] In a specific embodiment, the system for catalytic desorption of carbon dioxide used in the present disclosure is as follows Figure 2As shown, the system includes a desorber 11 and a boiler 12; the boiler 12 is provided with a first inlet and a first outlet; the first outlet of the boiler 12 is connected to the amine steam inlet e of the desorber 11, and the first inlet of the boiler 12 is connected to the amine liquid outlet b of the desorber 11; the boiler 12 is configured to provide heat to the desorber 11; the desorber 11 is configured to catalytically desorb the CO2-rich amine liquid using a filler.

[0045] The wire mesh demister and tubular distributor involved in the present disclosure are devices of conventional structures in the art. The device structures involved in the present disclosure that have not been improved, such as the wire mesh demister, tubular distributor, graded flow liquid inlet, regeneration gas outlet, liquid replenishment port, pressure relief port, sewage outlet, temperature detection port, pressure detection port, sampling port, flue gas test port, external steam inlet and condensate outlet.

[0046] Using this disclosure Figure 2 The specific process flow of the system shown includes: external steam first enters the boiler 12 through the external steam inlet 16, and then part of the CO2-rich amine liquid in the desorption tower 11 enters the boiler 12 through the amine liquid outlet b, and the temperature of the CO2-rich amine liquid is increased through indirect heat exchange. Then, the amine steam after indirect heat exchange enters the desorption tower 11 through the amine steam inlet e, and the CO2-rich amine liquid in the desorption tower 11 is fully contacted and reacted with the filler under the stirring of the reaction stirring device 8, and is desorbed into a lean liquid under the action of the catalyst and discharged from the desorption tower 11 through the lean liquid outlet c, and the desorbed CO2 is discharged from the desorption tower 11 through the regeneration gas outlet d, and the steam in the boiler 12 is condensed into condensed water and discharged from the system through the condensed water outlet 17.

[0047] The present disclosure is further illustrated below by way of examples, but the present disclosure is not limited thereby.

[0048] In the following examples of the present disclosure, SiO2, B2O3 and TiO2 are purchased from Shanghai Aladdin Co., Ltd. Unless otherwise specified, the chemical reagents used in the present disclosure are all commercially available products.

[0049] Example 1 S1: Active ingredient SiO2 with a purity of 99wt% and matrix material TiO2 are mixed in a weight ratio of 1:6, and then stirred in pyridine. The weight ratio of active ingredient SiO2 to pyridine is 1:0.05, the temperature is 30°C, the stirring time is 12h, the stirring rate is 300rpm, and then the first product is obtained; wherein the pore size of SiO2 is 1~20nm, and the particle size is 5~10nm; the average particle size of matrix material TiO2 is 0.1nm~50nm, the average pore size is 1nm~20nm, and the BET specific surface area is 1~1000m 2 / g, pore volume 0.01~10cm 3 / g; S2: The first product obtained in S1 is subjected to molding, curing and drying to obtain a ceramic filler; the ceramic filler is formed into a corrugated plate type; the curing treatment conditions include: a temperature of 35°C and a time of 12 hours; the drying treatment conditions include a temperature of 25°C and a time of 12 hours.

[0050] Based on the total weight of the ceramic filler, the ceramic filler includes 80 wt % of TiO2, 13 wt % of SiO2 and 7 wt % of pyridine loaded on the matrix. The average particle size of the ceramic filler is 12 nm. Example 2 The method of this embodiment is the same as that of embodiment 1, except that the active ingredient used in S1 is B2O3 and the organic dopant is piperazine.

[0051] Based on the total weight of the ceramic filler, the ceramic filler includes 90 wt % of TiO2, 5 wt % of B2O3 and 5 wt % of piperazine loaded on the matrix, the pore size of B2O3 is 10-15 nm, and the average particle size of the ceramic filler is 12 nm. Comparative Example 1 The method of this comparative example is the same as that of Example 1, except that no organic dopant is added, the weight ratio of the active ingredient to the matrix material in S1 is 1:2, and the obtained ceramic filler includes 95 weight % TiO2 and 5 weight % SiO2 loaded on the matrix.

[0052] Test Case The ceramic fillers of Examples 1-2 and Comparative Example 1 were added to the desorption tower to desorb the CO2-rich amine solution. The concentration of the amine solution used for desorption was 25%, and the rich liquid load was a monoethanolamine solution (MEA) of 0.5 mol CO2 / mol amine. The desorption energy consumption (GJ / tCO2) defines the energy required to desorb 1 ton of carbon dioxide, and the heat is provided by steam. The desorption temperature and energy consumption are shown in Table 1.

[0053] Test case using Figure 1The desorption tower shown in the figure has a wire mesh demister 1 arranged at the top of the desorption tower to reduce the volatilization of CO2-rich amine liquid and the carrying of CO2-rich amine liquid by the regenerated gas CO2 when it is discharged, thereby reducing the loss of CO2-rich amine liquid. A tubular distributor 9 is arranged above each packing layer to promote the uniform distribution of CO2-rich amine liquid on the packing. The packing unit 4 includes a first packing layer, a second packing layer and a third packing layer. A packing pressure ring 3 is arranged on the top of each packing layer, and a packing support 7 is arranged on the bottom, and the packing layer is filled with packing. The spacing between two adjacent packing layers is 1 to 6 meters. The liquid distributor 2 is a trough-disc type liquid distributor, which is conducive to the uniform distribution of CO2-rich amine liquid on the packing. The filter screen 5 is arranged on the upper part of the liquid distributor 2 to avoid the tower The flow of internal filler; the reaction stirring device 8 includes a stirring paddle, the desorption tower is provided with a stirring port, the stirring paddle includes a connected stirring rod and a stirring blade, the stirring rod extends from the stirring port of the desorption tower from the outside of the tower into the inside of the tower so that the stirring blade is located in the amine liquid reaction chamber of the desorption tower; a part of the stirring rod is located outside the desorption tower to connect the motor; the height of the amine liquid reaction chamber is 0.5~5m, the stirring port is arranged on the tower wall of the amine liquid reaction chamber, and the height distance between the stirring port and the bottom of the lower head of the desorption tower is 0.5~2m; the amine liquid outlet b, the thermal siphon return liquid port T and the amine vapor inlet e are arranged longitudinally in sequence on the tower wall of the amine liquid reaction chamber; the flash steam inlet i and the amine vapor port h are arranged in the same horizontal direction; the amine liquid outlet b is higher than the amine vapor inlet e 0.1~2m; the hot siphon liquid return port T is 0.2~2m higher than the amine steam inlet e; the boiler interface o is arranged at the lower part of the flash steam inlet i, and the distance from the flash steam inlet i is 0.5~2m; the stirring port is arranged below the amine steam port h, and the spacing is 0.3~1m.

[0054] like Figure 2 As shown, the specific process flow of the system disclosed in the present invention includes: external steam first enters the boiler 12 through the external steam inlet 16, and then part of the CO2-rich amine liquid in the desorption tower 11 enters the boiler 12 through the amine liquid outlet b, and the temperature of the CO2-rich amine liquid is increased through indirect heat exchange. Then, the amine steam after indirect heat exchange enters the desorption tower 11 through the amine steam inlet e, and the CO2-rich amine liquid in the desorption tower 11 is fully contacted and reacted with the filler under the stirring of the reaction stirring device 8, and the reaction stirring device 8 can be a stirring paddle. At the same time, under the action of the catalyst, the lean liquid is desorbed and discharged from the desorption tower 11 through the lean liquid outlet c, and the desorbed CO2 is discharged from the desorption tower 11 through the regeneration gas outlet d, and the steam in the boiler 12 is condensed into condensed water and discharged from the system through the condensed water outlet 17.

[0055] Table 1

[0056] From the data in Table 1, it can be seen that the use of the ceramic filler disclosed in the present invention can reduce the reaction barrier, reduce the desorption temperature and regeneration energy consumption. By comparing Example 1 and Example 2, it can be seen that when the preferred active ingredient of the present invention is B2O3, the obtained ceramic filler has a better effect of reducing the desorption temperature and regeneration energy consumption. The preferred embodiments of the present disclosure are described in detail above in conjunction with the accompanying drawings; however, the present disclosure is not limited to the specific details in the above embodiments. Within the technical concept of the present disclosure, a variety of simple modifications can be made to the technical solution of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.

[0057] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present disclosure will not further describe various possible combinations.

[0058] In addition, various embodiments of the present disclosure may be arbitrarily combined, and as long as they do not violate the concept of the present disclosure, they should also be regarded as the contents disclosed by the present disclosure.

Claims

1. A ceramic filler for catalytic desorption of carbon dioxide, characterized in that: The ceramic filler comprises 70-95 wt % of a matrix material, 0.8-20 wt % of an active ingredient loaded on the matrix material, and 0.3-15 wt % of an organic dopant, based on the total weight of the ceramic filler; The matrix material comprises one or more porous materials; the active ingredient is selected from one or more metal oxides and non-metal oxides; wherein the metal is selected from one or more elements of Group IIIA, Group IVB and Group VIII, and the non-metal is selected from one or more elements of Group IIIA and Group IVA.

2. The ceramic filler according to claim 1, wherein The ceramic filler comprises 90-95 wt % of a matrix material, 0.8-5 wt % of an active ingredient and 0.3-5 wt % of an organic dopant loaded on the matrix, based on the total weight of the ceramic filler; Optionally, the weight ratio of the matrix material to the active ingredient is 9-6:1, preferably 8-7:

1.

3. The ceramic filler according to claim 1, wherein The matrix material is selected from one or more of titanium dioxide and molecular sieves, and the molecular sieve is selected from one or more of ZSM molecular sieves, Y molecular sieves and HZ molecular sieves; preferably titanium dioxide; preferably, the matrix material has an average particle size of 0.1nm to 50nm, an average pore size of 1nm to 20nm, and a BET specific surface area of ​​1 to 1000m 2 / g, pore volume 0.01~10cm 3 / g; Optionally, the metal oxide is selected from one or more of Al2O3, ZrO2, Fe2O3 and Fe3O4, and the non-metal oxide is selected from one or more of B2O3 and SiO2; preferably B2O3; the pore size of SiO2 is 2-50nm, preferably 1nm-20nm; the average particle size of SiO2 is 1-20nm, preferably 5-10nm; Optionally, the organic dopant includes piperazine and / or pyridine.

4. The ceramic filler according to claim 1, wherein The ceramic filler is formed into a structured filler or a random filler; the filler form of the structured filler includes one or more of a plate type, a corrugated plate type and a honeycomb type; the filler form of the random filler includes one or more of a triple Y ring, a Raschig ring, a cross partition ring, a Pall ring, a rectangular saddle ring, an isotropic saddle ring, a conjugate ring and a flat ring.

5. A method for preparing a ceramic filler for catalytic desorption of carbon dioxide, characterized in that: The steps include: S1, contacting the matrix material with the active component in the organic dopant to load the active component and the organic dopant to obtain a first product; S2, subjecting the first product to molding, curing and drying processes; The matrix material comprises one or more porous materials; the active ingredient comprises one or more metal oxides and non-metal oxides; the metal is selected from one or more of Group IIIA, Group IVB and Group VIII, and the non-metal is selected from one or more of Group IIIA and Group IVA.

6. The method according to claim 5, wherein: The organic dopant includes piperazine and / or pyridine; The weight ratio of the organic dopant to the active ingredient is 0.01-3:1, preferably 0.1-1:

1.

7. The method according to claim 5, wherein: In step S1, the matrix material and the active ingredient are added in a weight ratio of 9 to 6:1, preferably 8 to 7:1; The matrix material is selected from one or more of titanium dioxide and molecular sieves, and the molecular sieve is selected from one or more of ZSM molecular sieves, Y molecular sieves and HZ molecular sieves; preferably titanium dioxide; Optionally, the metal oxide is selected from one or more of Al2O3, ZrO2, Fe2O3 and Fe3O4; the non-metal oxide is selected from one or more of B2O3 and SiO2; preferably B2O3.

8. The method according to claim 5, wherein: The contact conditions in step S1 include a contact temperature of 0 to 50° C., preferably 10 to 30° C.; a contact time of 4 to 24 hours, preferably 6 to 16 hours; and a stirring rate of 100 to 600 rpm, preferably 200 to 400 rpm.

9. The method according to claim 5, wherein: In step S2, the drying treatment conditions include a temperature of 100-400°C, preferably 110-200°C; a time of 6-40 hours, preferably 8-18 hours; The curing treatment conditions include a temperature of 0 to 60° C., preferably 15 to 30° C., and a time of 3 to 24 hours, preferably 6 to 16 hours.

10. A ceramic filler for catalytic desorption of carbon dioxide prepared according to the method of any one of claims 5 to 9.

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