Fe / Cu-SAPO-11 adsorption carrier for adsorbing NH3 and resisting SO2 poisoning as well as preparation method and application of Fe / Cu-SAPO-11 adsorption carrier

Abstract

The invention discloses a Fe / Cu-SAPO-11 adsorption carrier capable of adsorbing NH3 and resisting poisoning as well as a preparation method and application of the Fe / Cu-SAPO-11 adsorption carrier, and belongs to the field of environmental pollution control materials and technologies. The preparation method at least comprises the following steps: in the presence of a source containing aluminum, phosphorus and silicon, performing hydrothermal synthesis, calcining to obtain an SAPO-11 molecular sieve, and finally loading copper by an ion exchange method. And carrying out hydrothermal synthesis on iron oxide, and physically mixing the molecular sieve and the iron oxide to obtain the Fe / Cu-SAPO-11. The Fe / Cu-SAPO-11 prepared in the invention has a micron-scale spherical structure, and iron oxide loaded on the Fe / Cu-SAPO-11 has a regular hexagonal structure with a nano-scale size. Compared with the prior art, the method disclosed by the invention is simple to operate, easy for large-scale production, high in NH3 adsorption efficiency and good in sulfur resistance.

Description

Technical Field

[0001] This invention belongs to the technical field of environmental pollution control materials, and specifically relates to an adsorption... And resist Poisoned Fe / Cu-SAPO-11 adsorbent carrier, its preparation method and application. Background Technology

[0002] Porous materials, as functional supports, play a crucial role in chemical processes such as catalysis, adsorption, and separation. Their performance hinges on their ability to provide efficient and stable enrichment and activation interfaces for target reactant molecules. For example, in many gas-solid phase catalytic reactions, the pre-adsorption and activation capacity of the support for reactants directly determines the catalyst's activation temperature, reaction efficiency, and anti-interference performance.

[0003] In the catalytic reduction process, As a key reducing agent, its effective adsorption is crucial for enhancing NO levels. x Catalytic reduction efficiency is a crucial prerequisite. However, actual exhaust gases contain... will with Competition for adsorption sites leads to changes in the reaction surface structure, causing blockage of the molecular sieve channels and severely affecting the channel efficiency. Therefore, developing highly efficient adsorption sites is crucial. Adsorption capacity and excellent resistance Adsorbent materials with anti-toxic properties have significant practical implications.

[0004] Currently, SAPO-34 and SSZ-13 with CHA structure, SSZ-39 with AEI structure, SSZ-16 with AFX structure, and ZK-5 with KFI structure have been reported to be effective in generating [the desired effect]. Adsorption. These molecular sieves possess complex pores and a large specific surface area, effectively enhancing the mass transfer and diffusion properties of reactants. As adsorbent supports, they are widely used in catalytic reactions. However, in practical applications, the presence of certain substances in flue gas is unavoidable. , The adsorption process during the catalytic reaction can cause a poisoning effect, which significantly reduces the adsorption performance of the material.

[0005] Molecular sieves, as porous materials, provide ideal supports for reactant enrichment and catalytic processes due to their regular channels and tunable acidity. Among them, SAPO-11, with its unique AEL structure, abundant acidity, and good thermal stability, is particularly suitable for loading... Significant potential in active components, and It exhibits both high reactivity and selectivity in reactions such as nitrogen oxide reduction. However, in industrial flue gas... Sulfur poisoning can easily lead to the deactivation of molecular sieves, severely limiting their practical applications. Studies have shown that introducing Fe components can preferentially adsorb... And to alleviate the poisoning of active sites. Therefore, this study aims to develop a SAPO-11 adsorbent carrier co-modified by Fe and Cu, by integrating high efficiency The adsorption activation capacity and the sulfur resistance properties of the Fe component enable ammonia adsorption with both high adsorption capacity and excellent stability in sulfur-containing atmospheres. Summary of the Invention

[0006] To address the problems of existing technologies, the present invention aims to provide an adsorption... And resist Poisoned Fe / Cu-SAPO-11 Adsorbent Carrier, Its Preparation Method, and Its Application. The preparation method of this invention is simple to operate, easy to scale up for production, and the obtained adsorbent carrier has the advantages of sulfur poisoning resistance and high adsorption efficiency.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0008] Firstly, the present invention provides an adsorption... And resist The preparation method of the poisoned Fe / Cu-SAPO-11 adsorbent includes the following steps:

[0009] Step (1): Dissolve aluminum source and phosphorus source in deionized water and stir. Then add di-n-propylamine and silicon source and continue stirring to form a gel. Transfer the gel to a polytetrafluoroethylene-lined reactor and heat it to pre-crystallize. Then continue to heat it to crystallize. After cooling, wash and dry. Calcine the powder in air, cool it naturally, wash it with ethanol, and dry it to obtain SAPO-11.

[0010] Step (2): SAPO-11 is sealed and heated in NH4Cl solution for ion exchange, centrifuged and washed, and then sealed and heated with copper salt aqueous solution for ion exchange. The product is collected by centrifugation and dried to obtain Cu-SAPO-11.

[0011] Step (3): Dissolve iron salt and sodium acetate in ethanol, then add deionized water, seal the mixed solution in a polytetrafluoroethylene-lined reactor, crystallize under hydrothermal conditions, cool and wash the precipitate, and dry to obtain α-Fe2O3.

[0012] Step (4): Mix and vibrate the synthesized Cu-SAPO-11 and α-Fe2O3 to obtain Fe / Cu-SAPO-11.

[0013] As a preferred embodiment, in step (1), the initial gel molar ratio of aluminum source, phosphorus source, silicon source, di-n-propylamine, and deionized water is (0.084~0.126):(0.062~0.138):(0.022~0.046):(0.1~0.144):(3~8).

[0014] As a preferred embodiment, in step (2), the concentration of NH4Cl is 0.8~1.4 M and the concentration of copper solution is 0.8~1.4 M.

[0015] As a preferred embodiment, in step (3), the molar ratio of iron salt, sodium acetate, ethanol and deionized water is (0.008~0.012):(0.096~0.106):(1.6~1.8):(0.38~0.42).

[0016] As a preferred embodiment, in step (4), the mass ratio of Cu-SAPO-11 to α-Fe2O3 is 1 to 9.

[0017] As a preferred embodiment, in step (1), the aluminum source is selected from boehmite, diatomite, or aluminum sulfate; the phosphorus source is selected from phosphoric acid; and the silicon source is selected from tetraethoxysilane or sodium silicate.

[0018] As a preferred embodiment, in step (1), the stirring time for aluminum source, phosphorus source and deionized water is 3-6 hours at a speed of 600 rpm, and the stirring time after adding di-n-propylamine and silicon source is 2-4 hours at a speed of 600 rpm; the pre-crystallization temperature is 100 ℃-140 ℃, the pre-crystallization time is 8-15 hours, the crystallization temperature is 180 ℃-200 ℃, the crystallization time is 30-60 hours; the calcination temperature is 600 ℃-800 ℃, and the calcination time is 6-8 hours.

[0019] As a preferred embodiment, in step (2), the copper salt is a copper-containing nitrate, chloride, or sulfate; the NH4Cl exchange temperature is 60 ℃~100 ℃, and the ion exchange time in the copper salt aqueous solution is 6~12 hours.

[0020] As a preferred embodiment, in step (3), the iron salt is an iron-containing nitrate, chloride, or acetate, and the reaction time is 8 to 16 hours.

[0021] Secondly, the present invention provides an adsorption And resist Fe / Cu-SAPO-11 adsorbent prepared by a method for preparing poisoned Fe / Cu-SAPO-11 adsorbent.

[0022] Thirdly, the present invention provides an adsorption And resist Application of Fe / Cu-SAPO-11 prepared by a method for preparing poisoned Fe / Cu-SAPO-11 adsorbent support, wherein the Fe / Cu-SAPO-11 is used for efficient and selective adsorption. and applicable Selective catalysis scenarios.

[0023] In this invention, the adsorption carrier is evaluated using the following method:

[0024] The Fe / Cu-SAPO-11 adsorbent was further evaluated using dynamic breakthrough experiments. Adsorption performance, and C represents the outlet. concentration, express Initial concentration. At the outlet The concentration reaches 5% of the initial concentration (i.e., C / ). When the concentration reaches 5%, determine its breakthrough adsorption capacity and breakthrough time; when the outlet concentration reaches 80% of the initial concentration (i.e., C / 5%), determine its breakthrough adsorption capacity and breakthrough time. When the adsorption rate is 80%, determine its saturated adsorption capacity. The total gas flow rate is set to 3000 mL / min, of which 500 ppm... N2 serves as the equilibrium gas.

[0025] Prior to activity evaluation, the adsorbent carrier underwent pretreatment: it was pretreated for 1 hour at 200°C in a 3000 mL / min N2 stream to remove surface and pore impurities. The outlet gas concentration was determined by... Gas monitor for measurement

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] This invention loads copper ions, an active factor, into SAPO-11 molecular sieves via ion exchange, thereby enhancing the acidity of SAPO-11. Compared to traditional impregnation methods, ion exchange methods can more fully activate copper ions. The prepared Cu-SAPO-11 possesses high activity sites, and Cu... 2+ The method boasts a high content ratio. By preparing specific concentrations, it can better determine the loading amount of active components. The method is simple and easy to operate, with a short ion exchange time, significantly improving production efficiency. Simultaneously, it ensures uniform distribution of copper ions within the molecular sieve, enhancing the stability and activity of the adsorbent support, thus providing stronger support for the catalytic process.

[0028] This invention employs a physical mixing method to prepare Fe / Cu-SAPO-11, which allows control over the morphology and properties of iron during the synthesis of iron oxide. The physical mixing process facilitates control over the content of the incorporated iron oxide and ensures a uniform distribution of the iron oxide.

[0029] Therefore, this material has broad application prospects in harsh catalytic processes such as sulfur-containing waste gas treatment and catalytic conversion of low-carbon alkanes in sulfur-containing atmospheres, and can significantly extend the service life of catalysts and improve the stability of process. Attached Figure Description

[0030] Figure 1 It is the highly efficient adsorbent prepared in Example 1 And resist XRD pattern of the poisoned Fe / Cu-SAPO-11 adsorbent.

[0031] Figure 2 It is the highly efficient adsorbent prepared in Example 1 And resist SEM image of the poisoned Fe / Cu-SAPO-11 adsorbent.

[0032] Figure 3 It is the highly efficient adsorbent prepared in Example 1 And resist XPS fit plot of Cu on the poisoned Fe / Cu-SAPO-11 adsorbent support.

[0033] Figure 4 It is the highly efficient adsorbent prepared in Example 1 And resist BET plot of poisoned Fe / Cu-SAPO-11 adsorbent.

[0034] Figure 5 The highly efficient adsorbents prepared in Examples 1-2 And resist Poisoned Fe / Cu-SAPO-11 adsorbent and comparative examples 1-2 Penetration curve.

[0035] Figure 6 The highly efficient adsorbents prepared in Examples 1-2 And resist The poisoned Fe / Cu-SAPO-11 adsorbent carrier compared with comparative examples 1-2 Under existing working conditions Penetration curve. Detailed Implementation

[0036] The present invention will be further described below with reference to embodiments.

[0037] Example 1

[0038] An adsorption method in this embodiment And resist The preparation method of the poisoned Fe / Cu-SAPO-11 adsorbent includes the following steps:

[0039] Step 1: Dissolve 10.377 g of boehmite in 75 mL of deionized water, stir well, and then add 15.68 g of phosphoric acid dropwise. Stir the mixture at 600 rpm for 4 hours. Then add 9.69 g of di-n-propylamine and 4.99 g of tetraethoxysilane dropwise, and stir at 600 rpm for 2 hours to obtain a gel. Transfer the gel to a polytetrafluoroethylene-lined reactor and pre-crystallize at 120 °C for 12 hours, followed by direct crystallization at 200 °C for 48 hours. Wash the crystallized sample several times with deionized water, then calcine at 600 °C for 6 hours in air. After cooling, wash with ethanol and deionized water, and dry to obtain SAPO-11 molecular sieve.

[0040] Step 2: The SAPO-11 obtained in Step 1 was immersed in a 1 M ammonium chloride aqueous solution for ion exchange at 80 °C for 8 hours, collected by centrifugation, washed, and dried. Subsequently, the obtained NH4-SAPO-11 was immersed in a 1 M copper chloride solution for ion exchange at 80 °C for 8 hours, and dried to obtain Cu-SAPO-11.

[0041] Step 3: Dissolve 1.08 g of FeCl3·6H2O and 3.32 g of sodium acetate in 40 mL of ethanol, then add 3 mL of deionized water dropwise. After stirring thoroughly, seal the mixture in a polytetrafluoroethylene-lined reactor and maintain it at 180 °C for 12 hours to obtain a red product. Centrifuge, wash several times, and dry at 80 °C to obtain α-Fe2O3.

[0042] Step 4: Take 0.7 g of Cu-SAPO-11 obtained in Step 2 and mix it with 0.3 g of α-Fe2O3 obtained in Step 3, shake for 1 h to obtain Fe / Cu-SAPO-11.

[0043] The breakthrough curve of the adsorbent carrier obtained in this embodiment is as follows: Figure 5 As shown.

[0044] Example 2

[0045] An adsorption method in this embodiment And resist The preparation method of the poisoned Fe / Cu-SAPO-11 adsorbent includes the following steps:

[0046] Step 1: Dissolve 15 g of boehmite in 80 mL of deionized water, stir well, then add 15 g of phosphoric acid dropwise. Stir the mixture for 4 hours, then add 9.69 g of di-n-propylamine and 3 g of sodium silicate dropwise, stirring for 2 hours to obtain a gel. Transfer the gel to a polytetrafluoroethylene-lined reactor and pre-crystallize at 120 °C for 12 hours, then directly raise the temperature to 200 °C for 48 hours. Wash the crystallized sample several times with deionized water, then calcine at 600 °C for 6 hours in air. After cooling, wash with ethanol and deionized water, and dry to obtain SAPO-11 molecular sieve.

[0047] Step 2: The SAPO-11 obtained in Step 1 was immersed in a 1 M ammonium sulfate aqueous solution for ion exchange at 80 °C for 8 hours, collected by centrifugation, washed, and dried. Subsequently, the prepared NH4-SAPO-11 was immersed in a 1 M copper sulfate solution for ion exchange at 80 °C for 8 hours, and dried to obtain Cu-SAPO-11.

[0048] Step 3: Add 1g of 3.32 g of sodium acetate was dissolved in 40 mL of ethanol, followed by the addition of 3 mL of deionized water. After thorough stirring, the mixture was sealed in a polytetrafluoroethylene-lined reactor and kept at 180 °C for 12 hours to obtain a red product. The product was centrifuged, washed several times, and dried at 80 °C to obtain α-Fe₂O₃.

[0049] Step 4: Take 0.7 g of Cu-SAPO-11 obtained in Step 2 and mix it with 0.3 g of α-Fe2O3 obtained in Step 3, shake for 0.5 h, and obtain Fe / Cu-SAPO-11.

[0050] The breakthrough curve of the adsorbent carrier obtained in this embodiment is as follows: Figure 5 As shown.

[0051] Example 3

[0052] An adsorption method in this embodiment And resist The preparation method of the poisoned Fe / Cu-SAPO-11 adsorbent includes the following steps:

[0053] Step 1: Dissolve 12.043 g of gibbsite in 78 mL of deionized water, stir well, and then add 15.68 g of phosphoric acid. Stir the mixture at 600 rpm for 6 hours. Then add 9.69 g of di-n-propylamine and 4.99 g of tetraethoxysilane, and stir at 600 rpm for 4 hours to obtain a gel. Transfer the gel to a polytetrafluoroethylene-lined reactor and pre-crystallize at 140 °C for 8 hours, followed by direct crystallization at 200 °C for 60 hours. Wash the crystallized sample several times with deionized water, then calcine at 800 °C for 8 hours in air. After cooling, wash with ethanol and deionized water, and dry to obtain SAPO-11 molecular sieve.

[0054] Step 2: The SAPO-11 obtained in Step 1 was immersed in a 1 M ammonium chloride aqueous solution for ion exchange at 60 °C for 6 hours, collected by centrifugation, washed, and dried. Subsequently, the obtained NH4-SAPO-11 was immersed in a 1 M copper nitrate solution for ion exchange at 80 °C for 6 hours, and dried to obtain Cu-SAPO-11.

[0055] Step 3: Add 1.61 g of 3.32 g of sodium acetate was dissolved in 40 mL of ethanol, followed by the addition of 3 mL of deionized water. After thorough stirring, the mixture was sealed in a polytetrafluoroethylene-lined reactor and kept at 190 °C for 8 hours to obtain a red product. The product was centrifuged, washed several times, and dried at 80 °C to obtain α-Fe₂O₃.

[0056] Step 4: Take 0.7 g of Cu-SAPO-11 obtained in Step 2 and mix it with 0.3 g of α-Fe2O3 obtained in Step 3, shake for 2 h to obtain Fe / Cu-SAPO-11.

[0057] The breakthrough curve of the adsorbent carrier obtained in this embodiment is as follows: Figure 5 As shown

[0058] Example 4

[0059] An adsorption method in this embodiment And resist The preparation method of the poisoned Fe / Cu-SAPO-11 adsorbent includes the following steps:

[0060] Step 1: Dissolve 26.41 g of aluminum sulfate in 90 mL of deionized water, stir well, and then add 15.68 g of phosphoric acid dropwise. Stir the mixture at 600 rpm for 3 hours. Then add 9.69 g of di-n-propylamine and 2.93 g of sodium silicate dropwise, and stir at 600 rpm for 2 hours to obtain a gel. Transfer the gel to a polytetrafluoroethylene-lined reactor and pre-crystallize at 100 °C for 15 hours, followed by direct crystallization at 180 °C for 30 hours. Wash the crystallized sample several times with deionized water, then calcine it at 800 °C for 8 hours in air. After cooling, wash with ethanol and deionized water, and dry to obtain SAPO-11 molecular sieve.

[0061] Step 2: The SAPO-11 obtained in Step 1 was immersed in a 1 M ammonium chloride aqueous solution for ion exchange at 100 °C for 12 hours, collected by centrifugation, washed, and dried. Subsequently, the prepared NH4-SAPO-11 was immersed in a 1 M copper chloride solution for ion exchange at 80 °C for 12 hours, and dried to obtain Cu-SAPO-11.

[0062] Step 3: Add 1.61 g of 3.32 g of sodium acetate was dissolved in 40 mL of ethanol, followed by the addition of 3 mL of deionized water. After thorough stirring, the mixture was sealed in a polytetrafluoroethylene-lined reactor and kept at 200 °C for 16 hours to obtain a red product. The product was centrifuged, washed several times, and dried at 80 °C to obtain α-Fe₂O₃.

[0063] Step 4: Take 0.7 g of Cu-SAPO-11 obtained in Step 2 and mix it with 0.3 g of α-Fe2O3 obtained in Step 3, shake for 1.5 h, and obtain Fe / Cu-SAPO-11.

[0064] The breakthrough curve of the adsorbent carrier obtained in this embodiment is as follows: Figure 5 As shown.

[0065] Comparative Example 1

[0066] The Cu-SAPO-11 molecular sieve adsorbent obtained in step (2) of Example 1 is used as the adsorbent in this comparative example and is labeled as Comparative Example 1.

[0067] The breakthrough curve of the adsorbent carrier obtained in this embodiment is as follows: Figure 5 As shown.

[0068] Comparative Example 2

[0069] In this comparative example, 0.7 g of Cu-SAPO-11 molecular sieve adsorbent obtained in step (2) of Example 1 was added dropwise to 3.76 mL of 1 M ferric nitrate solution, allowed to stand for 12 hours, dried, and then calcined in air at 500 °C for 4 hours. The adsorbent obtained after grinding was labeled as Comparative Example 2.

[0070] The breakthrough curve of the obtained adsorbent carrier is as follows: Figure 5 As shown.

[0071] Performance Characterization

[0072] The samples prepared in Example 1 were physically characterized using TEM, SEM, XRD, and BET methods.

[0073] Experiment 1 was conducted on the adsorbents prepared in Examples 1-4 and Comparative Examples 1-2. The evaluation of the penetration test is as follows:

[0074] The prepared adsorbent carrier was subjected to treatment in a fixed-bed quartz reactor. Breakthrough experiment. The total gas flow rate was 1200 mL / min, and the gas composition was 2000 ppm. , As a balance gas. Before the adsorption experiment, the adsorption support was heated to 200 °C. Pre-treatment in the stream for 1 hour was performed to remove surface impurities. Subsequently, the reactor temperature was stabilized to 200 °C, and a stream containing... The mixed gas was analyzed, and the outlet concentration was determined using an ammonia gas detector. [The remaining text appears to be incomplete and requires further context.] ] in Indicates the inlet ammonia concentration, [ ] out Indicates the concentration of ammonia gas at the outlet. Adsorption efficiency on the adsorption carrier Calculated using the following formula:

[0075]

[0076] Adsorption capacity was determined by analyzing the breakthrough curve and calculating its integral, as shown in Table 1.

[0077]

[0078] Table 1

[0079] For Experiment 1, the catalytic conversion results of the examples and comparative examples are as follows: Figure 5 As shown.

[0080] Experiment 2 tested the adsorbents prepared in Examples 1-4 and Comparative Examples 1-2. The sulfur resistance was evaluated using a penetration test, and the evaluation method is as follows:

[0081] The prepared adsorbent carrier was subjected to treatment in a fixed-bed quartz reactor. Breakthrough experiment. The total gas flow rate was 1200 mL / min, and the gas composition was 2000 ppm. 500 ppm , As a balance gas. Before the adsorption experiment, the adsorption support was heated to 200 °C. Pre-treatment in the stream for 1 hour was performed to remove surface impurities. Subsequently, the reactor temperature was stabilized to 200 °C, and a stream containing... The concentration of the mixed gas at the outlet was determined using an ammonia gas detector. The adsorption efficiency on the adsorption carrier is calculated by the following formula:

[0082]

[0083] The adsorption capacity was determined by analyzing the breakthrough curve and calculating its integral, as shown in Table 2.

[0084]

[0085] Table 2

[0086] For Experiment 2, the catalytic conversion results of the examples and comparative examples are as follows: Figure 6 As shown.

[0087] Depend on Figure 5 As shown in Table 1, the adsorption carriers of Examples 1-4 and Comparative Example 1 exhibited high adsorption capacity in flue gas without sulfur interference. However, Comparative Example 2, in which iron ions were directly loaded into the molecular sieve, showed a lower adsorption capacity, possibly because iron oxide within the pores blocked the internal channels of the molecular sieve.

[0088] Depend on Figure 6 As shown in Table 2, the adsorption carriers of Examples 1-4 and Comparative Example 1 maintained high adsorption capacity in flue gas with sulfur interference. However, the adsorption capacity of Comparative Example 1, which did not contain iron, decreased sharply. A possible reason for this is... The effect on adsorption sites. Therefore, the Fe / Cu-SAPO-11 adsorbent not only has excellent adsorption performance, but also good... Resistance to poisoning.

[0089] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. An adsorption And resist A method for preparing a poisoned Fe / Cu-SAPO-11 adsorbent carrier, characterized in that, Includes the following steps: Step (1): Dissolve aluminum source and phosphorus source in deionized water and stir. Then add di-n-propylamine and silicon source and continue stirring to form a gel. Transfer the gel to a polytetrafluoroethylene-lined reactor and heat it to pre-crystallize. Then continue to heat it to crystallize. After cooling, wash and dry. Calcine the powder in air, cool it naturally, wash it with ethanol, and dry it to obtain SAPO-11. Step (2): SAPO-11 is sealed and heated in NH4Cl solution for ion exchange, centrifuged and washed, and then sealed and heated with copper salt aqueous solution for ion exchange. The product is collected by centrifugation and dried to obtain Cu-SAPO-11. Step (3): Dissolve iron salt and sodium acetate in ethanol, then add deionized water, seal the mixed solution in a polytetrafluoroethylene-lined reactor, crystallize under hydrothermal conditions, cool and wash the precipitate, and dry to obtain α-Fe2O3. Step (4): Mix and vibrate the synthesized Cu-SAPO-11 and α-Fe2O3 to obtain Fe / Cu-SAPO-11.

2. The adsorption according to claim 1 And resist A method for preparing a poisoned Fe / Cu-SAPO-11 adsorbent carrier, characterized in that, In step (1), the initial gel molar ratio of aluminum source, phosphorus source, silicon source, di-n-propylamine, and deionized water is (0.084~0.126):(0.062~0.138):(0.022~0.046):(0.1~0.144):(3~8). In step (2), the concentration of NH4Cl is 0.8~1.4 M, and the concentration of copper solution is 0.8~1.4 M; In step (3), the molar ratio of iron salt, sodium acetate, ethanol and deionized water is (0.008~0.012):(0.096~0.106):(1.6~1.8):(0.38~0.42). In step (4), the mass ratio of Cu-SAPO-11 to α-Fe2O3 is 1 to 9.

3. The adsorption according to claim 1 And resist A method for preparing a poisoned Fe / Cu-SAPO-11 adsorbent carrier, characterized in that, In step (1), the aluminum source is selected from boehmite, diatomite, or aluminum sulfate; the phosphorus source is selected from phosphoric acid; and the silicon source is selected from tetraethoxysilane or sodium silicate.

4. The adsorption according to claim 1 And resist A method for preparing a poisoned Fe / Cu-SAPO-11 adsorbent carrier, characterized in that, In step (1), the aluminum source and phosphorus source are stirred with deionized water for 3-6 hours at a speed of 600 rpm. After adding di-n-propylamine and silicon source, the stirring time is 2-4 hours at a speed of 600 rpm. The pre-crystallization temperature is 100 ℃-140 ℃, the pre-crystallization time is 8-15 hours, the crystallization temperature is 180 ℃-200 ℃, and the crystallization time is 30-60 hours. The calcination temperature is 600 ℃-800 ℃, and the calcination time is 6-8 hours.

5. The adsorption according to claim 1 And resist A method for preparing a poisoned Fe / Cu-SAPO-11 adsorbent carrier, characterized in that, In step (2), the copper salt is a copper-containing nitrate, chloride, or sulfate; the NH4Cl exchange temperature is 60 ℃~100 ℃, the exchange time is 6~12 hours, and the ion exchange time in the copper salt aqueous solution is 6~12 hours.

6. The adsorption according to claim 1 And resist A method for preparing a poisoned Fe / Cu-SAPO-11 adsorbent carrier, characterized in that, In step (3), the iron salt is an iron-containing nitrate, chloride, or acetate, and the reaction time is 8 to 16 hours.

7. The adsorption according to claim 1 And resist A method for preparing a poisoned Fe / Cu-SAPO-11 adsorbent carrier, characterized in that, In step (4), the sealing and shaking time of α-Fe2O3 and Cu-SAPO-11 is 0.5 to 2 hours.

8. The adsorbent prepared according to any one of the preparation methods of claims 1-7 And resist Poisoned Fe / Cu-SAPO-11 adsorbent.

9. The adsorbent prepared according to any one of claims 1-7 And resist The application of the poisoned Fe / Cu-SAPO-11 adsorbent carrier is characterized by, Applied to In the existing environment Adsorption.

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