An oxygen carrier for oxidative degradation of organic amines and a preparation method and application thereof

Abstract

The present application relates to the technical field of oxygen carrier, and particularly relates to an oxygen carrier for oxidative degradation of organic amine, a preparation method and application thereof. The oxygen carrier comprises a core layer and a shell layer coated on the core layer; the shell layer comprises ZrO2 and a perovskite oxide ABO 3‑δ ; A in the perovskite oxide ABO 3‑δ comprises La and Sr, B comprises Cu and an auxiliary element, and the auxiliary element is Fe and / or Mn. The oxygen carrier can oxidize the organic amine into nitrogen and water, and high selectivity and reaction efficiency can be achieved in the reaction.

Description

Technical Field

[0001] This invention relates to the field of oxygen carrier technology, and in particular to an oxygen carrier for the oxidative degradation of organic amines, its preparation method, and its application. Background Technology

[0002] In large-scale carbon capture and storage (CCUS) technology systems in the thermal power industry, the organic amine chemical absorption method has become the most widely used carbon dioxide capture scheme due to its high capture efficiency and relatively mature technical route. Organic amine absorbents, represented by monoethanolamine (MEA) and diethanolamine (DEA), undergo a reversible reaction with carbon dioxide in flue gas in the absorption tower, and then release high-purity carbon dioxide products through thermal drive in the regeneration tower. However, this regeneration process has become a weak link in the system operation: under high-temperature desorption conditions, some organic amines escape with the carbon dioxide products in the form of aerosols or vapors, forming an unavoidable "amine escape" phenomenon. These organic amines entrained in high-purity carbon dioxide not only reduce the purity of the carbon dioxide products but also trigger a series of environmental risks. Escaped amines can participate in photochemical reactions in the atmosphere, generating highly carcinogenic nitrosamines, and both the amines themselves and their degradation products pose potential threats to ecosystems and human health. With the continuous expansion of carbon capture scale, the cumulative environmental effects of amine escape are becoming increasingly prominent, becoming a major bottleneck restricting the sustainable development of this technology.

[0003] To address the problem of amine escape, existing technologies mainly employ two treatment routes: physical and chemical methods. Physical methods include condensation recovery, adsorption capture, and membrane separation. However, these methods have limited efficiency when treating low-concentration, high-flow-rate amine vapors, and adsorbent regeneration is difficult, while membrane materials are prone to aging. Chemical methods include high-temperature thermal oxidation and low-temperature plasma. Among these, chemical looping technology, as an important branch of high-temperature thermal oxidation, achieves the directional transfer of oxygen through the recycling of oxygen carriers, avoiding the introduction of air or gaseous oxygen. However, research on chemical looping technology in the treatment of amine pollutants is still insufficient. Oxygen carriers used in reactions such as partial oxidation and catalytic reforming of tar (e.g., patent CN121338758A) and methane combustion for hydrogen production (e.g., patent CN114477299A) have been reported, but oxygen carriers suitable for the oxidative degradation of organic amines have not yet been reported. Furthermore, the selective oxidation of reactants by oxygen carriers is highly correlated with the elemental composition of the oxygen carrier. Oxygen carriers designed for other reactions are unlikely to achieve high selectivity when used for the oxidative degradation of organic amines. Summary of the Invention

[0004] To address the aforementioned technical problems, there is currently no oxygen carrier specifically designed for the oxidative degradation of organic amines, and oxygen carriers designed for other reactions often fail to achieve high selectivity when used for the oxidative degradation of organic amines. This invention provides an oxygen carrier for the oxidative degradation of organic amines, its preparation method, and its applications. The oxygen carrier of this invention can oxidize and degrade organic amines into non-polluting nitrogen and water, achieving high selectivity and reaction efficiency in this reaction.

[0005] The specific technical solution of this invention is as follows: In a first aspect, the present invention provides an oxygen carrier for the oxidative degradation of organic amines, comprising a core layer and a shell layer covering the core layer; the shell layer comprises ZrO2 and perovskite oxide ABO. 3-δ The perovskite oxide ABO 3-δ In this context, A includes La and Sr, and B includes Cu and auxiliary elements, with the auxiliary elements being Fe and / or Mn.

[0006] In the general formula of the perovskite oxide of this invention, "δ" represents the oxygen vacancy concentration. During the oxidative degradation of organic amines and the regeneration of the oxygen carrier after the oxidative degradation of organic amines, the value of "δ" changes as the reaction proceeds.

[0007] In the perovskite oxide contained in the oxygen carrier of this invention, La, as an A-site element, supports the entire perovskite structure; Sr, as an A-site dopant, introduces charge mismatch and lattice distortion, increases oxygen vacancies (δ), and lowers the lattice oxygen migration barrier, making it easier for the reaction to enter the redox cycle involving lattice oxygen, thereby regulating the reaction rate. Furthermore, for the specific reaction of the oxidative degradation of organic amines into nitrogen and water, this invention uses Cu at the B-site of the perovskite oxide, combined with specific auxiliary elements (Fe and / or Mn), which helps to achieve higher reactivity and selectivity (reducing byproducts such as NO). x The specific mechanism for its generation is as follows: The selective oxidative degradation mechanism of organic amines under the action of an oxygen carrier in this invention can be roughly summarized as follows: amine adsorption / coordination at the B-site → lattice oxygen-induced dehydrogenation to generate a nitrogen-containing intermediate → CN-clast fragmentation and deep oxidation of the carbon framework → surface coupling and desorption of nitrogen-containing species to N2. The Cu element at the B-site has a stronger activation ability for amine nitrogen and is more likely to trigger local lattice oxygen release and selective oxidation of organic amines, thereby lowering the onset temperature and increasing the low-temperature reaction rate. However, if its local "oxygen supply intensity" is too high, it may cause the nitrogen-containing intermediate to proceed to the peroxidation side pathway (NO2). xThe precursors lead to lower reaction selectivity; Fe at the B site tends to participate in stepwise oxidation with milder lattice oxygen, and the selectivity of stepwise oxidation is stronger under lattice oxygen enrichment conditions, which can improve N2 selectivity kinetically, but also makes it more sensitive to sulfur-containing impurities; Mn sites have a wider range of reversible valence states and stronger defect recovery ability. Although higher temperatures are required to fully activate oxygen migration, they are more conducive to replenishing lattice oxygen and restoring oxygen vacancy distribution during the regeneration stage, thereby improving the cycle regeneration capacity. In the oxygen carrier, Cu preferentially generates functional groups / nitrogen-containing intermediates and oxygen vacancies at low temperatures. Fe / Mn tends to guide these intermediates to N2 coupling desorption channels and buffer the excessive oxidation intensity of Cu. At the same time, Mn accelerates the recovery of oxygen vacancies and lattice oxygen during the cycle, thus achieving a balance between activity and selectivity.

[0008] Using a specific perovskite oxide ABO 3-δ Building upon this foundation, the present invention further introduces ZrO2 into the shell, which can form fluorite phase La at the interface through an oxidation reaction stage. 0.5 Zr 0.5 O 2-x During the reduction stage, ZrO2 can accommodate and disperse oxygen vacancies, preventing excessive local oxygen loss in the main body. During the regeneration stage, it can preferentially replenish oxygen and feed oxygen back to the perovskite. Furthermore, ZrO2 is less likely to introduce excessively strong surface-active oxygen, leading to the peroxidation of nitrogen-containing intermediates. Therefore, the introduction of ZrO2 into the shell can improve the effective oxygen supply of the oxygen carrier while maintaining the oxidation selectivity of organic amines.

[0009] Preferably, the perovskite oxide ABO 3-δ In this mixture, the molar ratio of La to Sr is 1.5~9.0:1, and the molar ratio of Cu to auxiliary elements is 0.1~2.0:1; in the shell layer, the perovskite oxide ABO 3-δ The mass ratio of ZrO2 to ZrO2 is 35:15~25.

[0010] When the molar ratio of Cu to auxiliary elements is 0.1~2.0:1, and perovskite oxide ABO 3-δ When the mass ratio of oxygen carrier to ZrO2 is 35:15~25, the oxygen carrier can better balance reactivity and selectivity when used in the reaction of organic amine oxidative degradation to produce nitrogen and water.

[0011] Preferably, the auxiliary elements are Fe and Mn, and the molar ratio of Fe to Mn is 0.5~1.5:1.

[0012] When Cu, Fe, and Mn are present at the B site, the selectivity and efficiency of the oxidative degradation of organic amines into nitrogen and water are improved to a greater extent compared to the presence of only Cu and Fe or only Cu and Mn.

[0013] Preferably, the core layer comprises Al2O3, SiO2 and ZrO2, wherein the mass percentage of Al2O3 is 50-70%, the mass percentage of SiO2 is 10-20%, and the mass percentage of ZrO2 is 10-30%.

[0014] Preferably, the shell further includes a binder, such as perovskite oxide ABO. 3-δ The mass ratio of the binder to the adhesive is 35:40~50; the adhesive includes Al2O3 and / or SiO2.

[0015] Preferably, the core layer has a particle size of 1.0~2.5 mm and the shell layer has a thickness of 20~500 μm.

[0016] Secondly, the present invention provides a method for preparing the oxygen carrier, the steps of which include: preparing a perovskite oxide ABO 3-δ Soluble salts of elements A and B, ZrO2 powder, and water are mixed to prepare a shell slurry. The core slurry is then coated onto the core surface and dried. The coating and drying steps are repeated 2-3 times. The mixture is then calcined and pre-activated by oxidation-reduction to obtain an oxygen carrier.

[0017] Thirdly, the present invention provides the application of the oxygen carrier in the removal of escaped organic amines in a carbon dioxide capture system, the steps of which include: contacting carbon dioxide containing organic amines with the oxygen carrier to carry out oxidative degradation of the organic amines.

[0018] Preferably, the oxidative degradation temperature is 500~580℃; the organic amine does not contain any metal elements.

[0019] Preferably, the organic amine includes one or more of monoethanolamine (MEA), diethanolamine (DEA), N-methyldiethanolamine (MDEA), and 2-amino-2-methyl-1-propanol (AMP).

[0020] Preferably, after the oxidative degradation of the organic amine is completed, the oxygen carrier is oxidatively regenerated under the action of oxygen; the oxygen carrier after oxidative regeneration is reused for the oxidative degradation of the organic amine; the temperature of the oxidative regeneration is 520~680℃.

[0021] Compared with the prior art, the present invention has the following advantages: (1) In the perovskite oxide contained in the oxygen carrier of the present invention, by using La and Sr elements at the A site and Cu, Fe and / or Mn elements at the B site, the reactivity and selectivity of the oxygen carrier in the oxidative degradation of organic amines can be improved.

[0022] (2) In the oxygen carrier of the present invention, by using perovskite oxide and ZrO2 in the shell layer, the oxygen carrier can have both high oxygen capacity and selectivity for organic amine oxidation degradation reaction. Attached Figure Description

[0023] Figure 1 This is a photograph of the oxygen carrier prepared in Example 1.

[0024] Figure 2 This is an electron microscope image of the surface of the oxygen carrier prepared in Example 1.

[0025] Figure 3 This is an electron microscope image of the cross-section of the oxygen carrier prepared in Example 1.

[0026] Figure 4 This is a photograph of the oxygen carrier prepared in Example 2.

[0027] Figure 5 This is an electron microscope image of the surface of the oxygen carrier prepared in Example 2.

[0028] Figure 6 This is a photograph of the oxygen carrier prepared in Example 3.

[0029] Figure 7 This is an electron microscope image of the surface of the oxygen carrier prepared in Example 3.

[0030] Figure 8 This is a photograph of the oxygen carrier prepared in Example 4.

[0031] Figure 9 This is an electron microscope image of the surface of the oxygen carrier prepared in Example 5.

[0032] Figure 10 The diagram shows the structure of the escaped organic amine capture device in Application Example 1 and Application Example 2.

[0033] The attached diagram is labeled as follows: 1. Organic amine conversion reactor; 2. Oxygen carrier regeneration reactor; 3. Amine-side cyclone separator; 4. Amine-side return valve; 5. Regeneration-side cyclone separator; 6. Regeneration-side return valve. Detailed Implementation

[0034] The present invention will be further described below with reference to embodiments.

[0035] First, the present invention relates to an oxygen carrier for the oxidative degradation of organic amines, comprising a core layer and a shell layer covering the core layer; the shell layer comprises ZrO2 and perovskite oxide ABO. 3-δ The perovskite oxide ABO 3-δ In this context, A includes La and Sr, and B includes Cu and auxiliary elements, with the auxiliary elements being Fe and / or Mn.

[0036] In some specific embodiments, the core layer includes Al2O3, SiO2 and ZrO2, wherein the mass percentage of Al2O3 is 50-70%, the mass percentage of SiO2 is 10-20%, and the mass percentage of ZrO2 is 10-30%.

[0037] In some specific embodiments, the perovskite oxide ABO 3-δ In this process, the molar ratio of La to Sr is 1.5 to 9.0:1, and the molar ratio of Cu to auxiliary elements is 0.1 to 2.0:1.

[0038] In some specific embodiments, the auxiliary elements are Fe and Mn, and the molar ratio of Fe to Mn is 0.5~1.5:1.

[0039] In some specific embodiments, the shell contains perovskite oxide ABO 3-δ The mass ratio of ZrO2 to ZrO2 is 35:15~25.

[0040] In some specific embodiments, the shell layer further includes a binder, a perovskite oxide (ABO). 3-δ The mass ratio of the binder to the adhesive is 35:40~50; the adhesive includes Al2O3 and / or SiO2.

[0041] In some specific embodiments, the core layer has a particle size of 1.0 to 2.5 mm and the shell layer has a thickness of 20 to 500 μm.

[0042] Second, the present invention relates to a method for preparing the oxygen carrier, the steps of which include: preparing a perovskite oxide ABO 3-δ Soluble salts of elements A and B, ZrO2 powder, and water are mixed to prepare a shell slurry. The core slurry is then coated onto the core surface and dried. The coating and drying steps are repeated 2-3 times. The mixture is then calcined and pre-activated by oxidation-reduction to obtain an oxygen carrier.

[0043] In some specific embodiments, a complexing agent is also added to the shell slurry, the complexing agent including polyethylene glycol and / or citric acid.

[0044] In some specific embodiments, the solid content of the shell slurry is 40~60wt%.

[0045] In some specific embodiments, the preparation steps of the core layer include: ball milling Al2O3 powder, SiO2 powder, ZrO2 powder, polymer binder, and water to obtain a core layer slurry, granulating and drying the slurry, and calcining it at 1200~1400℃ for 2~4 hours to obtain the core layer. Optionally or preferably, the polymer binder includes polyvinyl alcohol and / or hydroxypropyl methylcellulose, with a content of 1~5wt% in the core layer slurry; a dispersant, including sodium polyacrylate, is also added to the core layer slurry, with a content of 0.5~5wt%; and the solid content of the core layer slurry is 10~30wt%.

[0046] In some specific embodiments, the redox pre-activation step includes: [the process involves] [activation at 600-800°C for 200-400 hours]. -1 Reduction was carried out by introducing H2-containing gas at GHSV for 1-1.5 hours, followed by 200-400 h⁻¹ at 600-800℃. -1 Oxidation is carried out by introducing oxygen-containing gas at high air velocity (GHSV) for 1 to 1.5 hours.

[0047] Third, the present invention relates to the application of the oxygen carrier in the removal of escaped organic amines in a carbon dioxide capture system, the steps of which include: contacting carbon dioxide containing organic amines with the oxygen carrier to carry out oxidative degradation of the organic amines.

[0048] In some specific embodiments, the organic amine does not contain any metal elements, including but not limited to one or more of monoethanolamine (MEA), diethanolamine (DEA), N-methyldiethanolamine (MDEA) and 2-amino-2-methyl-1-propanol (AMP).

[0049] In some specific embodiments, the temperature of the oxidative degradation is 500~580℃.

[0050] In some specific embodiments, after the oxidative degradation of the organic amine is completed, the oxygen carrier is oxidatively regenerated under the action of oxygen; the oxygen carrier after oxidative regeneration is reused for the oxidative degradation of the organic amine; the temperature of the oxidative regeneration is 520~680℃.

[0051] The present invention will now be described through specific embodiments and comparative examples. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention.

[0052] Example 1 The oxygen carrier structure and composition used in this embodiment are as follows: it consists of a core layer and a shell layer covering the core layer; the core layer consists of Al2O3, SiO2, and ZrO2 in a mass ratio of 60:15:25; the shell layer consists of perovskite oxide La in a mass ratio of 35:15:50. 0.65 Sr0.35 Fe 0.85 Cu 0.15 O 3-δ It is composed of ZrO2 and Al2O3; the core layer has a particle size of 1.2~2.2 mm, and the shell layer has a thickness of 150~200 μm. This oxygen carrier is prepared according to the following steps (wherein the amount of each raw material is determined according to the composition of the core and shell layers): S1: Al2O3 powder, SiO2 powder, and ZrO2 powder were mixed, and deionized water and 3 wt% polyvinyl alcohol were added. The mixture was wet-milled in a ball mill for 6 hours to homogenize the slurry, resulting in a core layer slurry with a D50 of 10 μm, containing 20 wt% solids and 3 wt% polyvinyl alcohol. The core layer slurry was then spray-granulated to form spherical green particles. After drying at 110℃ for 3 hours, the particles were calcined in air at 1300℃ for 3 hours. After cooling to room temperature, the particles were sieved to obtain a core layer with a particle size of 1.2~2.2 mm.

[0053] S2: Lanthanum nitrate, strontium nitrate, ferric nitrate, copper nitrate, ZrO2 powder (D50 = 0.5 μm) and Al2O3 powder (D50 = 7 μm) are mixed, deionized water, citric acid and polyethylene glycol are added, and the mixture is ball-milled for 4 hours to make the slurry uniform, so as to obtain a shell slurry with a solid content of 40 wt%, a polyethylene glycol content of 0.3 wt%, and a citric acid content of 115 wt% of the total content of lanthanum ions, strontium ions, iron ions and copper ions.

[0054] S3: Place the core layer in a spin coating apparatus and apply the shell slurry to the surface of the core layer using a combination of immersion and rotation. Then dry at 85°C for 3 hours. Repeat the above coating and drying steps 3 times. Then calcine in an air atmosphere at 820°C for 2.5 hours and cool to room temperature to obtain core-shell structured particles.

[0055] S4: The core-shell structured particles were placed in a tube furnace and activated at 700°C for 1 hour by introducing a H2 / N2 mixture (with a hydrogen volume fraction of 5%), followed by nitrogen purging for 30 minutes. The H2 / N2 mixture was then replaced with air, and activation continued at 700°C for another hour. Throughout this process, the space velocity (GHSV) of both the H2 / N2 mixture and the air was set to 300 h⁻¹. -1 The heating rate was set to 8℃ / min. After completing the above process, it was naturally cooled to room temperature to obtain the oxygen carrier (denoted as "Al2O3-SiO2-ZrO2@La"). 0.65 Sr 0.35 Fe 0.85 Cu 0.15 O 3-δ -ZrO2-Al2O3”). The appearance of the oxygen carrier prepared in this embodiment is as follows. Figure 1 As shown, the surface morphology is as follows Figure 2 As shown, the cross-sectional morphology is as follows Figure 3 As shown.

[0056] Example 2 The oxygen carrier structure and composition used in this embodiment are as follows: it consists of a core layer and a shell layer covering the core layer; the core layer consists of Al2O3, SiO2, and ZrO2 in a mass ratio of 55:15:30; the shell layer consists of perovskite oxide La in a mass ratio of 35:25:40. 0.9 Sr 0.1 Cu 0.65 Mn 0.35 O 3-δ It is composed of ZrO2 and Al2O3; the core layer has a particle size of 1.0~2.0 mm, and the shell layer has a thickness of 100~150 μm. This oxygen carrier is prepared according to the following steps (wherein the amount of each raw material is determined according to the composition of the core and shell layers): S1: Al2O3 powder, SiO2 powder, and ZrO2 powder were mixed, and deionized water, polyvinyl alcohol, and 0.5 wt% sodium polyacrylate were added. The mixture was wet-milled in a ball mill for 6 hours to homogenize the slurry, resulting in a core layer slurry with a D50 of 10 μm, containing 30 wt% solids and 3 wt% polyvinyl alcohol. The core layer slurry was then spray-granulated to form spherical green particles. After drying at 110℃ for 3 hours, the particles were calcined in air at 1300℃ for 3 hours. After cooling to room temperature, the particles were sieved to obtain a core layer with a particle size of 1.0~2.0 mm.

[0057] S2: Lanthanum nitrate, strontium nitrate, copper nitrate, manganese nitrate, ZrO2 powder (D50 = 0.5 μm) and Al2O3 powder (D50 = 10 μm) are mixed, deionized water and citric acid are added, and the mixture is ball-milled for 4 hours to make the slurry uniform, so as to obtain a shell slurry with a solid content of 60 wt% and a citric acid content of 150 wt% of the total content of lanthanum ions, strontium ions, copper ions and manganese ions.

[0058] S3: The shell slurry is applied to the core surface by rotary spraying and then dried at 120°C for 3 hours. The above application and drying steps are repeated 3 times. Then, the core-shell structured particles are calcined in air at 900°C for 2.5 hours and cooled to room temperature to obtain the core-shell structured particles.

[0059] S4: The core-shell structured particles were placed in a tube furnace and activated at 700°C for 1 hour by introducing a H2 / N2 mixture (with a hydrogen volume fraction of 5%), followed by nitrogen purging for 30 minutes. The H2 / N2 mixture was then replaced with air, and activation continued at 700°C for another hour. Throughout this process, the space velocity (GHSV) of both the H2 / N2 mixture and the air was set to 300 h⁻¹. -1 The heating rate was set to 8℃ / min. After completing the above process, it was naturally cooled to room temperature to obtain the oxygen carrier (denoted as "Al2O3-SiO2-ZrO2@La"). 0.9 Sr 0.1 Cu 0.65 Mn 0.35 O 3-δ -ZrO2-Al2O3”). The appearance of the oxygen carrier prepared in this embodiment is as follows. Figure 4 As shown, the surface morphology is as follows Figure 5 As shown.

[0060] Example 3 The oxygen carrier structure and composition used in this embodiment are as follows: it consists of a core layer and a shell layer covering the core layer; the core layer consists of Al2O3, SiO2, and ZrO2 in a mass ratio of 60:15:25; the shell layer consists of perovskite oxide La in a mass ratio of 35:15:50. 0.65 Sr 0.35 Mn 0.85 Cu 0.15 O 3-δ It is composed of ZrO2 and Al2O3; the core layer has a particle size of 1.2~2.2 mm, and the shell layer has a thickness of 150~200 μm. This oxygen carrier is prepared according to the following steps (wherein the amount of each raw material is determined according to the composition of the core and shell layers): S1: Al2O3 powder, SiO2 powder, and ZrO2 powder were mixed, and deionized water and 3 wt% polyvinyl alcohol were added. The mixture was wet-milled in a ball mill for 6 hours to homogenize the slurry, resulting in a core layer slurry with a D50 of 10 μm, containing 20 wt% solids and 3 wt% polyvinyl alcohol. The core layer slurry was then spray-granulated to form spherical green particles. After drying at 110℃ for 3 hours, the particles were calcined in air at 1300℃ for 3 hours. After cooling to room temperature, the particles were sieved to obtain a core layer with a particle size of 1.2~2.2 mm.

[0061] S2: Lanthanum nitrate, strontium nitrate, manganese nitrate, copper nitrate, ZrO2 powder (D50 = 0.5 μm) and Al2O3 powder (D50 = 7 μm) are mixed, deionized water, citric acid and polyethylene glycol are added, and the mixture is ball-milled for 4 hours to make the slurry uniform, so as to obtain a shell slurry with a solid content of 40 wt%, a polyethylene glycol content of 0.3 wt%, and a citric acid content of 115 wt% of the total content of lanthanum ions, strontium ions, manganese ions and copper ions.

[0062] S3: Place the core layer in a spin coating apparatus and apply the shell slurry to the surface of the core layer using a combination of immersion and rotation. Then dry at 85°C for 3 hours. Repeat the above coating and drying steps 3 times. Then calcine in an air atmosphere at 820°C for 2.5 hours and cool to room temperature to obtain core-shell structured particles.

[0063] S4: The core-shell structured particles were placed in a tube furnace and activated at 700°C for 1 hour by introducing a H2 / N2 mixture (with a hydrogen volume fraction of 5%), followed by nitrogen purging for 30 minutes. The H2 / N2 mixture was then replaced with air, and activation continued at 700°C for another hour. Throughout this process, the space velocity (GHSV) of both the H2 / N2 mixture and the air was set to 300 h⁻¹. -1 The heating rate was set to 8℃ / min. After completing the above process, it was naturally cooled to room temperature to obtain the oxygen carrier (denoted as "Al2O3-SiO2-ZrO2@La"). 0.65 Sr 0.35 Mn 0.85 Cu 0.15 O 3-δ -ZrO2-Al2O3”). The appearance of the oxygen carrier prepared in this embodiment is as follows. Figure 6 As shown, the surface morphology is as follows Figure 7 As shown.

[0064] Example 4 The oxygen carrier structure and composition used in this embodiment are as follows: it consists of a core layer and a shell layer covering the core layer; the core layer consists of Al2O3, SiO2, and ZrO2 in a mass ratio of 60:15:25; the shell layer consists of perovskite oxide La in a mass ratio of 35:15:50. 0.65 Sr 0.35 Mn 0.45 Fe 0.4 Cu 0.15 O 3-δ It is composed of ZrO2 and Al2O3; the core layer has a particle size of 1.2~2.2 mm, and the shell layer has a thickness of 150~200 μm. This oxygen carrier is prepared according to the following steps (wherein the amount of each raw material is determined according to the composition of the core and shell layers): S1: Al2O3 powder, SiO2 powder, and ZrO2 powder were mixed, and deionized water and 3 wt% polyvinyl alcohol were added. The mixture was wet-milled in a ball mill for 6 hours to homogenize the slurry, resulting in a core layer slurry with a D50 of 10 μm, containing 20 wt% solids and 3 wt% polyvinyl alcohol. The core layer slurry was then spray-granulated to form spherical green particles. After drying at 110℃ for 3 hours, the particles were calcined in air at 1300℃ for 3 hours. After cooling to room temperature, the particles were sieved to obtain a core layer with a particle size of 1.2~2.2 mm.

[0065] S2: Lanthanum nitrate, strontium nitrate, manganese nitrate, ferric nitrate, copper nitrate, ZrO2 powder (D50 = 0.5 μm) and Al2O3 powder (D50 = 7 μm) are mixed, deionized water, citric acid and polyethylene glycol are added, and the mixture is ball-milled for 4 hours to make the slurry uniform, so as to obtain a shell slurry with a solid content of 40 wt%, a polyethylene glycol content of 0.3 wt%, and a citric acid content of 115 wt% of the total content of lanthanum ions, strontium ions, manganese ions, iron ions and copper ions.

[0066] S3: Place the core layer in a spin coating apparatus and apply the shell slurry to the surface of the core layer using a combination of immersion and rotation. Then dry at 85°C for 3 hours. Repeat the above coating and drying steps 3 times. Then calcine in an air atmosphere at 820°C for 2.5 hours and cool to room temperature to obtain core-shell structured particles.

[0067] S4: The core-shell structured particles were placed in a tube furnace and activated at 700°C for 1 hour by introducing a H2 / N2 mixture (with a hydrogen volume fraction of 5%), followed by nitrogen purging for 30 minutes. The H2 / N2 mixture was then replaced with air, and activation continued at 700°C for another hour. Throughout this process, the space velocity (GHSV) of both the H2 / N2 mixture and the air was set to 300 h⁻¹. -1 The heating rate was set to 8℃ / min. After completing the above process, it was naturally cooled to room temperature to obtain the oxygen carrier (denoted as "Al2O3-SiO2-ZrO2@La"). 0.65 Sr 0.35 Mn 0.45 Fe 0.4 Cu 0.15 O 3-δ -ZrO2-Al2O3”). The appearance of the oxygen carrier prepared in this embodiment is as follows. Figure 8 As shown, the surface morphology is as follows Figure 9 As shown.

[0068] Comparative Example 1 The oxygen carrier used in this comparative example has the following structure and composition: it consists of a core layer and a shell layer surrounding the core layer; the core layer consists of Al2O3, SiO2, and ZrO2 in a mass ratio of 60:15:25; the shell layer consists of perovskite oxide La in a mass ratio of 35:15:50. 0.65 Sr 0.35 FeO 3-δ It is composed of ZrO2 and Al2O3; the core layer has a particle size of 1.2~2.2 mm, and the shell layer has a thickness of 150~200 μm. This oxygen carrier is prepared according to the following steps (wherein the amount of each raw material is determined according to the composition of the core and shell layers): S1: Al2O3 powder, SiO2 powder, and ZrO2 powder were mixed, and deionized water and 3 wt% polyvinyl alcohol were added. The mixture was wet-milled in a ball mill for 6 hours to homogenize the slurry, resulting in a core layer slurry with a D50 of 10 μm, containing 20 wt% solids and 3 wt% polyvinyl alcohol. The core layer slurry was then spray-granulated to form spherical green particles. After drying at 110℃ for 3 hours, the particles were calcined in air at 1300℃ for 3 hours. After cooling to room temperature, the particles were sieved to obtain a core layer with a particle size of 1.2~2.2 mm.

[0069] S2: Lanthanum nitrate, strontium nitrate, ferric nitrate, ZrO2 powder (D50 = 0.5 μm) and Al2O3 powder (D50 = 7 μm) are mixed, and deionized water, citric acid and polyethylene glycol are added. The mixture is ball-milled for 4 hours to make the slurry uniform, and a shell slurry is obtained, in which the solid content is 40 wt%, the polyethylene glycol content is 0.3 wt%, and the citric acid content is 115 wt% of the total content of lanthanum ions, strontium ions and iron ions.

[0070] S3: Place the core layer in a spin coating apparatus and apply the shell slurry to the surface of the core layer using a combination of immersion and rotation. Then dry at 85°C for 3 hours. Repeat the above coating and drying steps 3 times. Then calcine in an air atmosphere at 820°C for 2.5 hours and cool to room temperature to obtain core-shell structured particles.

[0071] S4: The core-shell structured particles were placed in a tube furnace and activated at 700°C for 1 hour by introducing a H2 / N2 mixture (with a hydrogen volume fraction of 5%), followed by nitrogen purging for 30 minutes. The H2 / N2 mixture was then replaced with air, and activation continued at 700°C for another hour. Throughout this process, the space velocity (GHSV) of both the H2 / N2 mixture and the air was set to 300 h⁻¹. -1 The heating rate was set to 8℃ / min. After completing the above process, it was naturally cooled to room temperature to obtain the oxygen carrier (denoted as "Al2O3-SiO2-ZrO2@La"). 0.65 Sr 0.35FeO 3-δ -ZrO2-Al2O3”).

[0072] Comparative Example 2 The oxygen carrier used in this comparative example has the following structure and composition: it consists of a core layer and a shell layer surrounding the core layer; the core layer consists of Al2O3, SiO2, and ZrO2 in a mass ratio of 60:15:25; the shell layer consists of perovskite oxide La in a mass ratio of 35:15:50. 0.65 Sr 0.35 MnO 3-δ It is composed of ZrO2 and Al2O3; the core layer has a particle size of 1.2~2.2 mm, and the shell layer has a thickness of 150~200 μm. This oxygen carrier is prepared according to the following steps (wherein the amount of each raw material is determined according to the composition of the core and shell layers): S1: Al2O3 powder, SiO2 powder, and ZrO2 powder were mixed, and deionized water and 3 wt% polyvinyl alcohol were added. The mixture was wet-milled in a ball mill for 6 hours to homogenize the slurry, resulting in a core layer slurry with a D50 of 10 μm, containing 20 wt% solids and 3 wt% polyvinyl alcohol. The core layer slurry was then spray-granulated to form spherical green particles. After drying at 110℃ for 3 hours, the particles were calcined in air at 1300℃ for 3 hours. After cooling to room temperature, the particles were sieved to obtain a core layer with a particle size of 1.2~2.2 mm.

[0073] S2: Lanthanum nitrate, strontium nitrate, manganese nitrate, ZrO2 powder (D50 = 0.5 μm) and Al2O3 powder (D50 = 7 μm) are mixed, deionized water, citric acid and polyethylene glycol are added, and the mixture is ball-milled for 4 hours to make the slurry uniform, so as to obtain a shell slurry with a solid content of 40 wt%, a polyethylene glycol content of 0.3 wt%, and a citric acid content of 115 wt% of the total content of lanthanum ions, strontium ions and manganese ions.

[0074] S3: Place the core layer in a spin coating apparatus and apply the shell slurry to the surface of the core layer using a combination of immersion and rotation. Then dry at 85°C for 3 hours. Repeat the above coating and drying steps 3 times. Then calcine in an air atmosphere at 820°C for 2.5 hours and cool to room temperature to obtain core-shell structured particles.

[0075] S4: The core-shell structured particles were placed in a tube furnace and activated at 700°C for 1 hour by introducing a H2 / N2 mixture (with a hydrogen volume fraction of 5%), followed by nitrogen purging for 30 minutes. The H2 / N2 mixture was then replaced with air, and activation continued at 700°C for another hour. Throughout this process, the space velocity (GHSV) of both the H2 / N2 mixture and the air was set to 300 h⁻¹. -1The heating rate was set to 8℃ / min. After completing the above process, it was naturally cooled to room temperature to obtain the oxygen carrier (denoted as "Al2O3-SiO2-ZrO2@La"). 0.65 Sr 0.35 MnO 3-δ -ZrO2-Al2O3”).

[0076] Comparative Example 3 The oxygen carrier used in this comparative example has the following structure and composition: it consists of a core layer and a shell layer surrounding the core layer; the core layer consists of Al2O3, SiO2, and ZrO2 in a mass ratio of 60:15:25; the shell layer consists of perovskite oxide La in a mass ratio of 35:15:50. 0.65 Sr 0.35 CuO 3-δ It is composed of ZrO2 and Al2O3; the core layer has a particle size of 1.2~2.2 mm, and the shell layer has a thickness of 150~200 μm. This oxygen carrier is prepared according to the following steps (wherein the amount of each raw material is determined according to the composition of the core and shell layers): S1: Al2O3 powder, SiO2 powder, and ZrO2 powder were mixed, and deionized water and 3 wt% polyvinyl alcohol were added. The mixture was wet-milled in a ball mill for 6 hours to homogenize the slurry, resulting in a core layer slurry with a D50 of 10 μm, containing 20 wt% solids and 3 wt% polyvinyl alcohol. The core layer slurry was then spray-granulated to form spherical green particles. After drying at 110℃ for 3 hours, the particles were calcined in air at 1300℃ for 3 hours. After cooling to room temperature, the particles were sieved to obtain a core layer with a particle size of 1.2~2.2 mm.

[0077] S2: Lanthanum nitrate, strontium nitrate, copper nitrate, ZrO2 powder (D50 = 0.5 μm) and Al2O3 powder (D50 = 7 μm) are mixed, and deionized water, citric acid and polyethylene glycol are added. The mixture is ball-milled for 4 hours to make the slurry uniform, and a shell slurry is obtained, in which the solid content is 40 wt%, the polyethylene glycol content is 0.3 wt%, and the citric acid content is 115 wt% of the total content of lanthanum ions, strontium ions and copper ions.

[0078] S3: Place the core layer in a spin coating apparatus and apply the shell slurry to the surface of the core layer using a combination of immersion and rotation. Then dry at 85°C for 3 hours. Repeat the above coating and drying steps 3 times. Then calcine in an air atmosphere at 820°C for 2.5 hours and cool to room temperature to obtain core-shell structured particles.

[0079] S4: The core-shell structured particles were placed in a tube furnace and activated at 700°C for 1 hour by introducing a H2 / N2 mixture (with a hydrogen volume fraction of 5%), followed by nitrogen purging for 30 minutes. The H2 / N2 mixture was then replaced with air, and activation continued at 700°C for another hour. Throughout this process, the space velocity (GHSV) of both the H2 / N2 mixture and the air was set to 300 h⁻¹. -1 The heating rate was set to 8℃ / min. After completing the above process, it was naturally cooled to room temperature to obtain the oxygen carrier (denoted as "Al2O3-SiO2-ZrO2@La"). 0.65 Sr 0.35 CuO 3-δ -ZrO2-Al2O3”).

[0080] Comparative Example 4 The oxygen carrier used in this comparative example has the following structure and composition: it consists of a core layer and a shell layer surrounding the core layer; the core layer consists of Al2O3, SiO2, and ZrO2 in a mass ratio of 60:15:25; the shell layer consists of perovskite oxide La in a mass ratio of 50:50. 0.65 Sr 0.35 Fe 0.85 Cu 0.15 O 3-δ It is composed of Al2O3; the core layer has a particle size of 1.2–2.2 mm, and the shell layer has a thickness of 150–200 μm. This oxygen carrier is prepared according to the following steps (wherein the amount of each raw material is determined according to the composition of the core and shell layers): S1: Al2O3 powder, SiO2 powder, and ZrO2 powder were mixed, and deionized water and 3 wt% polyvinyl alcohol were added. The mixture was wet-milled in a ball mill for 6 hours to homogenize the slurry, resulting in a core layer slurry with a D50 of 10 μm, containing 20 wt% solids and 3 wt% polyvinyl alcohol. The core layer slurry was then spray-granulated to form spherical green particles. After drying at 110℃ for 3 hours, the particles were calcined in air at 1300℃ for 3 hours. After cooling to room temperature, the particles were sieved to obtain a core layer with a particle size of 1.2~2.2 mm.

[0081] S2: Lanthanum nitrate, strontium nitrate, ferric nitrate, copper nitrate and Al2O3 powder (D50 = 7 μm) are mixed, deionized water, citric acid and polyethylene glycol are added, and the mixture is ball-milled for 4 hours to make the slurry uniform, so as to obtain a shell slurry with a solid content of 40 wt%, a polyethylene glycol content of 0.3 wt%, and a citric acid content of 115 wt% of the total content of lanthanum ions, strontium ions, iron ions and copper ions.

[0082] S3: Place the core layer in a spin coating apparatus and apply the shell slurry to the surface of the core layer using a combination of immersion and rotation. Then dry at 85°C for 3 hours. Repeat the above coating and drying steps 3 times. Then calcine in an air atmosphere at 820°C for 2.5 hours and cool to room temperature to obtain core-shell structured particles.

[0083] S4: The core-shell structured particles were placed in a tube furnace and activated at 700°C for 1 hour by introducing a H2 / N2 mixture (with a hydrogen volume fraction of 5%), followed by nitrogen purging for 30 minutes. The H2 / N2 mixture was then replaced with air, and activation continued at 700°C for another hour. Throughout this process, the space velocity (GHSV) of both the H2 / N2 mixture and the air was set to 300 h⁻¹. -1 The heating rate was set to 8℃ / min. After completing the above process, it was naturally cooled to room temperature to obtain the oxygen carrier (denoted as "Al2O3-SiO2-ZrO2@La"). 0.65 Sr 0.35 Fe 0.85 Cu 0.15 O 3-δ -Al2O3”).

[0084] Comparative Example 5 The oxygen carrier used in this comparative example has the following structure and composition: it consists of a core layer and a shell layer surrounding the core layer; the core layer consists of Al2O3, SiO2, and ZrO2 in a mass ratio of 60:15:25; the shell layer consists of perovskite oxide La in a mass ratio of 35:15:50. 0.65 Sr 0.35 Fe 0.85 Cu 0.15 O 3-δ It is composed of CeO2 and Al2O3; the core layer has a particle size of 1.2~2.2 mm, and the shell layer has a thickness of 150~200 μm. This oxygen carrier is prepared according to the following steps (wherein the amount of each raw material is determined according to the composition of the core and shell layers): S1: Al2O3 powder, SiO2 powder, and ZrO2 powder were mixed, and deionized water and 3 wt% polyvinyl alcohol were added. The mixture was wet-milled in a ball mill for 6 hours to homogenize the slurry, resulting in a core layer slurry with a D50 of 10 μm, containing 20 wt% solids and 3 wt% polyvinyl alcohol. The core layer slurry was then spray-granulated to form spherical green particles. After drying at 110℃ for 3 hours, the particles were calcined in air at 1300℃ for 3 hours. After cooling to room temperature, the particles were sieved to obtain a core layer with a particle size of 1.2~2.2 mm.

[0085] S2: Lanthanum nitrate, strontium nitrate, ferric nitrate, copper nitrate, CeO2 powder (D50 = 0.5 μm) and Al2O3 powder (D50 = 7 μm) are mixed, deionized water, citric acid and polyethylene glycol are added, and the mixture is ball-milled for 4 hours to make the slurry uniform, so as to obtain a shell slurry with a solid content of 40 wt%, a polyethylene glycol content of 0.3 wt%, and a citric acid content of 115 wt% of the total content of lanthanum ions, strontium ions, iron ions and copper ions.

[0086] S3: Place the core layer in a spin coating apparatus and apply the shell slurry to the surface of the core layer using a combination of immersion and rotation. Then dry at 85°C for 3 hours. Repeat the above coating and drying steps 3 times. Then calcine in an air atmosphere at 820°C for 2.5 hours and cool to room temperature to obtain core-shell structured particles.

[0087] S4: The core-shell structured particles were placed in a tube furnace and activated at 700°C for 1 hour by introducing a H2 / N2 mixture (with a hydrogen volume fraction of 5%), followed by nitrogen purging for 30 minutes. The H2 / N2 mixture was then replaced with air, and activation continued at 700°C for another hour. Throughout this process, the space velocity (GHSV) of both the H2 / N2 mixture and the air was set to 300 h⁻¹. -1 The heating rate was set to 8℃ / min. After completing the above process, it was naturally cooled to room temperature to obtain the oxygen carrier (denoted as "Al2O3-SiO2-ZrO2@La"). 0.65 Sr 0.35 Fe 0.85 Cu 0.15 O 3-δ -CeO2-Al2O3”).

[0088] Application Example 1 The escaped organic amine capture device used in this application example is, for example... Figure 10As shown, the specific structure is as follows: it consists of an organic amine conversion reactor 1, an oxygen carrier regeneration reactor 2, an amine-side cyclone separator 3, an amine-side return valve 4, a regeneration-side cyclone separator 5, and a regeneration-side return valve 6. The organic amine conversion reactor 1 is a fluidized bed reactor with a diameter of 0.6 m and a height of 3.5 m. The oxygen carrier regeneration reactor 2 has a diameter of 0.5 m and a height of 3 m. Both the amine-side return valve 4 and the regeneration-side return valve 6 are U-shaped structures with an inner diameter of 0.12 m, and both have an N2 inlet at the bottom. The organic amine conversion reactor 1 has a CO2 gas inlet at the bottom, a reaction product outlet at the top, and a regenerated oxygen carrier inlet on the side; the oxygen carrier regeneration reactor 2 has an air inlet at the bottom, a regenerated product outlet at the top, and a reduced oxygen carrier inlet on the side; the reaction product outlet of the organic amine conversion reactor 1 is connected to the reduced oxygen carrier inlet of the oxygen carrier regeneration reactor 2 in sequence through an amine-side cyclone separator 3 and an amine-side return valve 4; the regenerated product outlet of the oxygen carrier regeneration reactor 2 is connected to the regenerated oxygen carrier inlet of the organic amine conversion reactor 1 in sequence through a regenerated-side cyclone separator 5 and a regenerated-side return valve 6; the pipelines in the entire device are made of high-temperature resistant stainless steel.

[0089] Flue gas from a coal-fired power plant is passed into an absorption tower containing an organic amine (monoethanolamine) solution. The organic amine solution absorbs carbon dioxide from the flue gas. The organic amine solution after carbon dioxide absorption is then passed into a regeneration tower, where heating regenerates the organic amine. The released CO2 stream contains escaped organic amine (the average concentration of monoethanolamine in the CO2 stream is 150 mg / m³). 3 The organic amine is then passed into the escape organic amine capture device of this application example to remove it. The device operation process is as follows: I) Load 60 kg of oxygen carrier into the organic amine conversion reactor. Nitrogen gas is introduced at a flow rate of 0.25 m / s through the N2 inlet of the amine-side return valve, the N2 inlet of the regeneration-side return valve, the CO2 gas flow inlet of the organic amine conversion reactor, and the air inlet of the oxygen carrier regeneration reactor. 3 Purge the entire gas path of the device for 20 minutes per hour to thoroughly remove residual air and moisture. After the oxygen carrier circulation in the escaped organic amine capture device has stabilized, continue to introduce nitrogen gas at the N2 inlet of the amine-side return valve and the regeneration-side return valve, and disconnect nitrogen gas input at other locations.

[0090] II) A CO2 gas stream containing organic amines is driven at a space velocity of 1500 h⁻¹ -1A CO2 gas stream is introduced into the organic amine conversion reactor through the inlet. The temperature at a bed height of 0.6 m is set to 580℃. The average upward velocity of the oxygen carrier within the reactor is controlled to be 1.1 m / s by adjusting the inlet gas velocity. Inside the reactor, the CO2 gas stream containing organic amines reacts with the oxygen carrier. The organic amines are oxidized and degraded into N2, CO2, and H2O, while the oxygen carrier is reduced and loses some lattice oxygen, transforming into a reduced oxygen carrier.

[0091] III) The gas flow after the reaction in the organic amine conversion reactor is output from the reaction product outlet at a flow rate of 0.4 m / s and enters the amine-side cyclone separator, where the reduced oxygen carrier is separated from the gas flow, and the purified CO2 is collected from the top outlet.

[0092] IV) The reduced oxygen carrier separated in the amine-side cyclone separator circulates at a rate of 1.2 kg / (m³). 2 •s) The reduced oxygen carrier is fed into the oxygen carrier regeneration reactor through the amine-side return valve, while air is simultaneously introduced from the air inlet at a space velocity of 800 h⁻¹. -1 In the input reactor, the temperature at a height of 1.2 m in the oxygen carrier regeneration reactor bed is set to 680℃. The average rising velocity of the oxygen carrier in the oxygen carrier regeneration reactor is controlled to be 0.7 m / s by controlling the air inlet velocity. Inside the oxygen carrier regeneration reactor, the reduced oxygen carrier undergoes an oxidation reaction upon contact with air, restoring its crystal structure and oxygen capacity.

[0093] V) The gas flow after regeneration in the oxygen carrier regeneration reactor is output from the regeneration product outlet and enters the regeneration side cyclone separator, where the regenerated oxygen carrier is separated from the gas flow and returned to the organic amine conversion reactor through the regeneration side return valve.

[0094] Using the oxygen carriers prepared in Examples 1, 3, and 4, and Comparative Examples 1-5, respectively, experiments were conducted according to the method described in this application example to detect monoethanolamine and NO at the inlet and outlet of the organic amine conversion reactor. x Concentration, conversion rate of monoethanolamine (MEA) after the system has stabilized, and NO concentration at the inlet and outlet. x Concentration difference (NO) x Concentration difference = NO at the outlet x Concentration - NO at the inlet x (Concentration), the results are shown in Table 1.

[0095] Table 1. Oxidative degradation efficiency and selectivity of organic amines in Application Example 1

[0096] Based on the test results in Table 1, it can be seen that: (1) The MEA conversion rate of Example 1 was higher than that of Comparative Example 1, and the MEA conversion rate of Example 3 was higher than that of Comparative Example 2; compared with Comparative Example 3, the NO at the inlet and outlet of Examples 1 and 3 was higher. x The concentration gradient is low. This indicates that the perovskite-type oxide ABO used in the oxygen carrier shell... 3-δ In this process, when Cu is used at the B-site in combination with Fe and / or Mn, it is beneficial to balance the activity and selectivity of the organic amine oxidative degradation reaction to produce nitrogen and water. The reason is that Cu at the B-site preferentially generates functional groups / nitrogen-containing intermediates and oxygen vacancies at low temperatures, which can lower the reaction onset temperature and increase the low-temperature reaction rate. Fe / Mn tends to guide this intermediate to the N2 coupling desorption channel and buffers the excessive oxidation intensity of Cu. At the same time, Mn accelerates the recovery of oxygen vacancies and lattice oxygen during the cycle. Therefore, the coexistence of Cu and Fe / Mn at the B-site is beneficial to achieving a balance between activity and selectivity.

[0097] (2) Compared with Comparative Example 4, the MEA conversion rate of both Example 1 and Comparative Example 5 was improved, while the NO at the inlet and outlet of Example 1 was lower. x The concentration difference is lower than that of Comparative Example 5. This indicates that introducing ZrO2 into the perovskite oxide shell can improve the degree of organic amine oxidative degradation and achieve higher reaction selectivity than CeO2. The reason for this is that ZrO2 and the perovskite oxide of this invention can form a fluorite phase La at the interface through an oxidation reaction stage. 0.5 Zr 0.5 O 2-x During the reduction phase, ZrO2 can accommodate and disperse oxygen vacancies, preventing excessive local oxygen loss in the main body. During the regeneration phase, it can preferentially replenish oxygen and feed oxygen back to the perovskite, thereby increasing the effective oxygen supply of the oxygen carrier. Furthermore, compared to CeO2, ZrO2 is less likely to introduce excessively strong surface-active oxygen, leading to the peroxidation of nitrogen-containing intermediates. Therefore, it can improve reaction selectivity and reduce the byproduct NO. x The formation of.

[0098] Application Example 2 The escaped organic amine capture device used in this application example has the same structure as in application example 1.

[0099] Flue gas from a coal-fired power plant is passed into an absorption tower containing an organic amine (monoethanolamine) solution. The organic amine solution absorbs carbon dioxide from the flue gas. The organic amine solution after carbon dioxide absorption is then passed into a regeneration tower, where heating regenerates the organic amine. The released CO2 stream contains escaped organic amines (the average concentration of monoethanolamine in the CO2 stream is 0.3 kg / t-CO2). This escaped organic amine is then passed into the escaped organic amine capture device in this application example to remove the organic amines. The device operation process is as follows: I) 220 kg of the oxygen carrier prepared according to the method of Example 2 was loaded into the organic amine conversion reactor, and 140 kg of the oxygen carrier prepared according to the method of Example 2 was loaded into the oxygen carrier regeneration reactor. Nitrogen gas was introduced into the reactor at a flow rate of 0.25 m³ / h from the N2 inlet of the amine-side return valve, the N2 inlet of the regeneration-side return valve, the CO2 gas flow inlet of the organic amine conversion reactor, and the air inlet of the oxygen carrier regeneration reactor. 3 Purge the entire gas path of the device for 20 minutes per hour to thoroughly remove residual air and moisture. After the oxygen carrier circulation in the escaped organic amine capture device has stabilized, continue to introduce nitrogen gas at the N2 inlet of the amine-side return valve and the regeneration-side return valve, and disconnect nitrogen gas input at other locations.

[0100] II) A CO2 gas stream containing organic amines is driven at a space velocity of 1500 h⁻¹ -1 A CO2 gas stream is introduced into the organic amine conversion reactor. The temperature at a bed height of 0.5 m is set to 500℃. The average upward velocity of the oxygen carrier within the reactor is controlled to be 0.75 m / s by adjusting the inlet gas velocity. Inside the reactor, the CO2 gas stream containing organic amines reacts with the oxygen carrier. The organic amines are oxidized and degraded into N2, CO2, and H2O, while the oxygen carrier is reduced and loses some lattice oxygen, transforming into a reduced oxygen carrier.

[0101] III) The gas flow after the reaction in the organic amine conversion reactor is output from the reaction product outlet at a flow rate of 0.4 m / s and enters the amine-side cyclone separator, where the reduced oxygen carrier is separated from the gas flow, and the purified CO2 is collected from the top outlet.

[0102] IV) The reduced oxygen carrier separated in the amine-side cyclone separator circulates at a rate of 1.2 kg / (m³). 2 •s) The reduced oxygen carrier is fed into the oxygen carrier regeneration reactor through the amine-side return valve, while air is simultaneously introduced from the air inlet at a space velocity of 800 h⁻¹. -1 In the input reactor, the temperature at a height of 1.0 m in the oxygen carrier regeneration reactor bed is set to 520℃, and the average rising velocity of the oxygen carrier in the oxygen carrier regeneration reactor is controlled to be 0.45 m / s by controlling the air inlet velocity. Inside the oxygen carrier regeneration reactor, the reduced oxygen carrier undergoes an oxidation reaction upon contact with air, restoring its crystal structure and oxygen capacity.

[0103] V) The gas flow after regeneration in the oxygen carrier regeneration reactor is output from the regeneration product outlet and enters the regeneration side cyclone separator, where the regenerated oxygen carrier is separated from the gas flow and returned to the organic amine conversion reactor through the regeneration side return valve.

[0104] Detection of monoethanolamine and NO at the inlet and outlet of the organic amine conversion reactor xConcentration, calculated after stable system operation, the conversion rate of monoethanolamine is 95%, and the NO at the outlet... x The concentration increased by 3 mg / m³ compared to the inlet. 3 .

Claims

1. An oxygen carrier for the oxidative degradation of organic amines, characterized in that, It includes a core layer and a shell layer covering the core layer; the shell layer includes ZrO2 and perovskite oxide ABO. 3-δ The perovskite oxide ABO 3-δ In this composition, A includes La and Sr, B includes Cu and auxiliary elements, the auxiliary elements being Fe and / or Mn; the core layer is composed of Al2O3, SiO2 and ZrO2.

2. The oxygen carrier according to claim 1, characterized in that, The perovskite oxide ABO 3-δ In this mixture, the molar ratio of La to Sr is 1.5~9.0:1, and the molar ratio of Cu to auxiliary elements is 0.1~2.0:1; in the shell layer, the perovskite oxide ABO 3-δ The mass ratio of ZrO2 to ZrO2 is 35:15~25.

3. The oxygen carrier according to claim 1 or 2, characterized in that, The auxiliary elements are Fe and Mn, and the molar ratio of Fe to Mn is 0.5~1.5:

1.

4. The oxygen carrier according to claim 1, characterized in that, In the core layer, Al2O3 accounts for 50-70% of the mass, SiO2 accounts for 10-20% of the mass, and ZrO2 accounts for 10-30% of the mass.

5. The oxygen carrier according to claim 1 or 2, characterized in that, The shell also includes a binder, a perovskite oxide ABO 3-δ The mass ratio of the binder to the adhesive is 35:40~50; the adhesive includes Al2O3 and / or SiO2.

6. The oxygen carrier according to claim 1, characterized in that, The core layer has a particle size of 1.0~2.5 mm, and the shell layer has a thickness of 20~500 μm.

7. A method for preparing an oxygen carrier according to any one of claims 1 to 6, characterized in that, step include: Perovskite oxide ABO 3-δ Soluble salts of elements A and B, ZrO2 powder, and water are mixed to prepare a shell slurry. The shell slurry is then coated onto the core surface and dried. The coating and drying steps are repeated 2-3 times. The mixture is then calcined and pre-activated by oxidation-reduction to obtain an oxygen carrier.

8. The application of the oxygen carrier according to any one of claims 1 to 6 in the removal of escaped organic amines in a carbon dioxide capture system, characterized in that, The steps include: Carbon dioxide containing organic amines is brought into contact with an oxygen carrier to oxidize and degrade the organic amines.

9. The application according to claim 8, characterized in that, The oxidative degradation temperature is 500~580℃; the organic amine does not contain any metal elements.

10. The application according to claim 8, characterized in that, After the oxidative degradation of the organic amine is completed, the oxygen carrier is oxidatively regenerated under the action of oxygen; the oxygen carrier after oxidative regeneration is reused for the oxidative degradation of the organic amine; the temperature of the oxidative regeneration is 520~680℃.

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