A method for preparing Fe / Mn-ZSM-5 type molecular sieve based on fischer-tropsch synthesis waste residue and application thereof

Abstract

The application discloses a kind of based on Fe-Ts synthesis waste residue preparation FeMn-ZSM-5 type molecular sieve method and application, belong to solid waste resource utilization technical field;The present method is with Fe-Ts synthesis waste residue as raw material by in-situ synthesis method with iron manganese bimetallic doped in molecular sieve framework, prepare Fe / Mn-ZSM-5 type molecular sieve;The present application is on the basis of guaranteeing that Si and Al in raw material participate in molecular sieve synthesis, with iron and manganese element doped in the molecular sieve framework, make it form new acid center, and combine with the metal ion on the surface of molecular sieve, increase catalyst surface active site;At the same time, due to Fe, Mn element is in the form of chemical bond in molecular sieve framework, form stable five-membered ring structure, and framework density is large, material stability is stronger;Fe / Mn-ZSM-5 type molecular sieve is used for heterogeneous fenton catalytic degradation of rhodamine B-containing wastewater.

Description

Technical Field

[0001] This invention belongs to the field of solid waste resource utilization technology, and relates to the preparation of molecular sieves. Specifically, it is a method for preparing Fe / Mn-ZSM-5 type molecular sieves using industrial solid waste Fischer-Tropsch synthesis residue as the main silicon, aluminum and iron source, as well as the application of this molecular sieve. Background Technology

[0002] Fischer-Tropsch synthesis waste is a solid waste generated during coal gasification, mainly composed of SiO2, Al2O3, and Fe2O3. If not properly disposed of, it will occupy a large amount of land, cause environmental pollution, and lead to resource waste. Therefore, it is urgent to find suitable treatment methods to utilize Fischer-Tropsch synthesis waste as a resource, thereby improving its treatment efficiency and added value. Currently, the resource utilization of Fischer-Tropsch synthesis waste mainly involves two aspects: one is using it directly as an adsorbent to remove heavy metals and other pollutants; the other is directly separating and recovering solid wax and spent catalysts from the waste. However, based on a literature review, no research has been found on synthesizing novel functional materials using Fischer-Tropsch synthesis waste as a raw material.

[0003] ZSM-5 molecular sieves, due to their unique pore structure, large specific surface area, and good chemical stability, are often used as catalysts in petroleum, chemical, and environmental protection fields. In particular, iron-based molecular sieve catalysts prepared by loading Fe onto ZSM-5 molecular sieves can play an important catalytic role in the catalytic oxidation of organic pollutants. Some existing patent documents report methods for preparing Fe-ZSM-5 molecular sieves. For example, patent document CN105964292A reports the preparation of ZSM-5 molecular sieves using chemical reagents via a hydrothermal method, followed by mixing with ferric nitrate solution and preparing Fe-ZSM-5 molecular sieves via ion exchange. However, in Fe-ZSM-5 molecular sieves synthesized by commonly used impregnation and ion exchange methods, the Fe is generally located on the outer surface or in the pores of the molecular sieve, resulting in weak catalytic activity and poor stability. Patent document CN115770609A reports a method for preparing Fe / ZSM-5 molecular sieves using fly ash. The fly ash undergoes high-temperature calcination, alkali activation, and acid leaching to remove impurities. An aluminum source and template agent are then added, followed by a hydrothermal reaction, washing, and drying to obtain the Fe / ZSM-5 molecular sieve. Overall, this method involves a complex synthesis process and high costs. In summary, Fe-ZSM-5 molecular sieves currently face two main bottlenecks: weak catalytic activity and poor stability, and high cost. Summary of the Invention

[0004] This invention overcomes the shortcomings of existing technologies, combines the main elemental composition of Fischer-Tropsch synthesis waste residue to develop novel functional catalysts, and proposes a method and application for preparing Fe / Mn-ZSM-5 molecular sieves based on Fischer-Tropsch synthesis waste residue.

[0005] To achieve the above objectives, the present invention is implemented through the following technical solution.

[0006] A method for preparing Fe / Mn-ZSM-5 molecular sieves based on Fischer-Tropsch synthesis waste includes the following steps:

[0007] 1) Remove organic components from the Fischer-Tropsch synthesis waste residue by roasting pretreatment for later use;

[0008] 2) Using Fischer-Tropsch synthesis waste as the silicon, aluminum, and iron source; with a molar ratio of n(SiO2):n(Al2O3):n(Fe2O3):n(Mn(NO3)2):n(Na2O):n(H2O):n(TPABr)=1:0.0067~0.02:0.0067~0.02:0.0067~0.02:0.08~0.2:30:0.2, add the pretreated Fischer-Tropsch synthesis waste, sodium hydroxide, silicon source, manganese source, water, and template agent. After mixing and stirring evenly, pour into a reaction vessel for crystallization reaction. After washing and drying, calcination is performed to remove the template agent, yielding Fe / Mn-ZSM-5 type molecular sieve.

[0009] Preferably, the roasting temperature of the Fischer-Tropsch synthesis waste residue in step 1) is 300~400℃ and the roasting time is 25~35min.

[0010] Preferably, the silicon source is silica sol.

[0011] Preferably, the manganese source is manganese nitrate.

[0012] Preferably, the template agent is tetrapropylammonium bromide.

[0013] Preferably, the crystallization reaction temperature is 170~190℃ and the crystallization time is 20~28h.

[0014] Preferably, the drying temperature is 100~120℃ and the drying time is 4~6h.

[0015] Preferably, the temperature for calcining to remove the template agent in step 2) is 500~600℃, and the calcination time is 4~6h.

[0016] Preferably, the reactor is a stainless steel reactor with a polytetrafluoroethylene liner.

[0017] The Fe / Mn-ZSM-5 molecular sieve prepared using the method described above for preparing Fe / Mn-ZSM-5 molecular sieve based on Fischer-Tropsch synthesis waste is used for heterogeneous Fenton catalytic degradation of wastewater containing Rhodamine B.

[0018] This invention, for the first time, utilizes Fischer-Tropsch synthesis waste as raw material to prepare Fe / Mn-ZSM-5 molecular sieves by in-situ synthesis of iron-manganese bimetallic doping onto a molecular sieve framework. Addressing the issues of weak catalytic activity and poor stability, this material, while ensuring the participation of Si and Al in the molecular sieve synthesis, incorporates iron and manganese into the molecular sieve framework, forming new acidic centers that combine with metal ions on the molecular sieve surface, increasing the number of active sites on the catalyst surface. Simultaneously, the redox cycle of Fe and Mn bimetals during degradation promotes electron transfer on the catalyst surface and the generation of active substances, thereby enhancing the catalytic activity of the molecular sieve. Furthermore, since Fe and Mn participate in the molecular sieve framework through chemical bonds, forming structurally stable five-membered rings with high framework density, the material exhibits stronger stability. Addressing the high cost of molecular sieve preparation, this material uses Fischer-Tropsch synthesis waste as a raw material to provide silicon, aluminum, and iron sources, reducing production costs from the source. The cost is nearly twice that of commercially available ZSM-5 molecular sieves, and the synthesis process eliminates the need for acid treatment and silicon / aluminum extraction, simplifying the process.

[0019] The beneficial effects of this invention compared to the prior art are as follows:

[0020] 1. This invention is the first to synthesize Fe / Mn-ZSM-5 molecular sieves using a one-step hydrothermal method based on silicon-aluminum and iron sources in Fischer-Tropsch synthesis waste residue. By introducing Fe and Mn elements into the molecular sieve framework, the catalytic performance of the material is improved, while production costs are reduced, thus achieving environmental protection, energy conservation and emission reduction, and a circular economy.

[0021] 2. The Fe / Mn-ZSM-5 molecular sieve obtained by this invention exhibits good crystallinity and a high specific surface area. The results of the embodiments show that the Fe / Mn-ZSM-5 molecular sieve provided by this invention has a relative crystallinity of 93% and a specific surface area of ​​365.16 m² / g, demonstrating broad application prospects and significant economic benefits.

[0022] 3. The Fe / Mn-ZSM-5 molecular sieve obtained by this invention has Fe and Mn participating in the molecular sieve framework, which improves the catalytic activity of the molecular sieve. When performing heterogeneous Fenton degradation of 10 mg / L Rhodamine B, the degradation rate of Rhodamine B was 98.39% after 60 min, and the degradation effect was obvious. Attached Figure Description

[0023] Figure 1 shows the XRD pattern of the Fe / Mn-ZSM-5 molecular sieve synthesized in Example 1.

[0024] Figure 2 is a SEM image of the Fe / Mn-ZSM-5 molecular sieve synthesized in Example 1.

[0025] Figure 3 shows the effect of the Fe / Mn-ZSM-5 molecular sieve synthesized in Example 1 on the degradation of Rhodamine B by H2O2.

[0026] Figure 4 shows the Fe / Mn-ZSM-5 molecular sieve synthesized in Example 1 and its Fe2p energy spectrum after adsorption and degradation of Rhodamine B; where (4a) is the Fe / Mn-ZSM-5 molecular sieve, (4b) is the Fe / Mn-ZSM-5 molecular sieve adsorbing Rhodamine B, and (4c) is the Fe / Mn-ZSM-5 molecular sieve after degradation of Rhodamine B.

[0027] Figure 5 shows the Fe / Mn-ZSM-5 molecular sieve synthesized in Example 1 and its Mn2p energy spectrum after adsorption and degradation; where (5a) is the Fe / Mn-ZSM-5 molecular sieve, (5b) is the Fe / Mn-ZSM-5 molecular sieve adsorbing Rhodamine B, and (5c) is the Fe / Mn-ZSM-5 molecular sieve after degrading Rhodamine B. Detailed Implementation

[0028] To make the technical problems to be solved, the technical solutions, and the beneficial effects of this invention clearer, the invention will be further described in detail with reference to the embodiments and accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. The technical solutions of this invention are described in detail below with reference to the embodiments and accompanying drawings, but the scope of protection is not limited thereto.

[0029] Example 1

[0030] Combination Figure 1-5 This embodiment proposes a method for preparing Fe / Mn-ZSM-5 molecular sieves based on Fischer-Tropsch synthesis waste. The Fischer-Tropsch synthesis waste used is a solid waste generated from the Fischer-Tropsch synthesis process in coal chemical production. The main components of its raw powder are diatomaceous earth, clay, and iron-containing waste catalyst. The main chemical components of the Fischer-Tropsch synthesis waste after calcination pretreatment are shown in Table 1. As can be seen from Table 1, the Fischer-Tropsch synthesis waste used in this embodiment has a high content of Si and Al, which can provide silicon and aluminum sources for the synthesis of molecular sieves. The presence of Fe can be used to synthesize Fe-based molecular sieve catalysts, which, together with the supplemented metal Mn bimetallic redox reaction, can enhance their catalytic activity.

[0031] ;

[0032] The chemical reagents used in this embodiment, such as tetrapropylammonium bromide (TPABr) and NaOH, are all of analytical grade.

[0033] The specific preparation steps for preparing Fe / Mn-ZSM-5 type zeolite molecular sieve based on Fischer-Tropsch synthesis waste in this embodiment are as follows:

[0034] S1: The Fischer-Tropsch synthesis waste residue is heated to 350°C in a muffle furnace and roasted for 30 minutes, then removed for later use.

[0035] It should be noted that the Fischer-Tropsch synthesis waste residue contains a high content of volatile organic wax components, which can adversely affect the synthesis of molecular sieves. If the Fischer-Tropsch synthesis waste residue is directly used for hydrothermal reactions, the impurities will reduce the conversion rates of Si and Al. Therefore, calcination to remove the organic wax components from the Fischer-Tropsch synthesis waste residue improves the activity of the raw material and is more conducive to the synthesis of molecular sieves.

[0036] S2: The Fischer-Tropsch synthesis waste residue after the above pretreatment is used to provide all aluminum source, iron source and part of silicon source, silica sol to supplement silicon source, and manganese nitrate as manganese source;

[0037] The molar ratio is:

[0038] The mixture of n(SiO2):n(Al2O3):n(Fe2O3):n(Mn(NO3)2):n(Na2O):n(H2O):n(TPABr) = 1:0.01:0.01:0.01:0.1:30:0.2 was prepared. Pretreated Fischer-Tropsch synthesis waste, sodium hydroxide, silicon source, manganese source, water, and tetrapropylammonium bromide were added and mixed thoroughly. The mixture was then transferred to a stainless steel reactor with a polytetrafluoroethylene liner and crystallized at 180°C for 24 hours. After cooling, filtration, washing, and drying at 105°C for 5 hours, the mixture was further processed.

[0039] S3: Finally, the dried sample was calcined in a muffle furnace at 550℃ for 5 hours to remove the template agent and obtain Fe / Mn-ZSM-5 molecular sieve.

[0040] The XRD pattern of the sample obtained in this embodiment shows that the synthesized molecular sieve exhibits obvious characteristic diffraction peaks of ZSM-5 type molecular sieves with strong peak intensity, and a relative crystallinity of 93%. Its scanning electron microscope image is shown in Figure 2. Its main morphology is approximately ellipsoidal, with plate-like rectangular structural units, uniform particle size, and regular morphology. BET characterization revealed that the Fe / Mn-ZSM-5 type molecular sieve synthesized in this embodiment has a large specific surface area of ​​365.16 m² / g, a pore volume of 0.23 cm³ / g, and an average pore size of 2.53 nm.

[0041] Example 2

[0042] This embodiment describes a method for preparing Fe / Mn-ZSM-5 molecular sieves based on Fischer-Tropsch synthesis waste. The method is essentially the same as in Example 1, and the preparation steps are briefly described below:

[0043] S1: The Fischer-Tropsch synthesis waste residue is heated to 350°C in a muffle furnace and roasted for 30 minutes, then removed for later use.

[0044] S2: Mass ratio:

[0045] The mixture of n(SiO2):n(Al2O3):n(Fe2O3):n(Mn(NO3)2):n(Na2O):n(H2O):n(TPABr) = 1:0.02:0.02:0.02:0.1:30:0.2 was prepared. Pretreated Fischer-Tropsch synthesis waste, sodium hydroxide, silicon source, manganese source, water, and tetrapropylammonium bromide were added. After stirring until homogeneous, the solid-liquid mixture was poured into a polytetrafluoroethylene liner and subjected to hydrothermal reaction in a stainless steel reactor. Crystallization was carried out at 180°C for 24 hours. After cooling, filtration, and washing, the mixture was dried at 105°C for 5 hours.

[0046] S3: Finally, the dried sample was calcined in a muffle furnace at 550℃ for 5 hours to remove the template agent and obtain Fe / Mn-ZSM-5 molecular sieve.

[0047] Example 3

[0048] This embodiment describes a method for preparing Fe / Mn-ZSM-5 molecular sieves based on Fischer-Tropsch synthesis waste. The method is essentially the same as in Example 1, and the preparation steps are briefly described below:

[0049] S1: The Fischer-Tropsch synthesis waste residue is heated to 350°C in a muffle furnace and roasted for 30 minutes, then removed for later use.

[0050] S2: Mass ratio:

[0051] The formula is: n(SiO2):n(Al2O3):n(Fe2O3):n(Mn(NO3)2):n(Na2O):n(H2O):n(TPABr) = 1:0.0067:0.0067:0.0067:0.1:30:0.2. Pretreated Fischer-Tropsch synthesis waste, sodium hydroxide, silicon source, manganese source, water, and tetrapropylammonium bromide are added, mixed, and stirred until homogeneous. This solid-liquid mixture is poured into a polytetrafluoroethylene liner and subjected to hydrothermal reaction in a stainless steel reactor. Crystallization is carried out at 180°C for 24 hours. After cooling, filtration, and washing, the mixture is dried at 105°C for 5 hours.

[0052] S3: Finally, the dried sample was calcined in a muffle furnace at 550℃ for 5 hours to remove the template agent and obtain Fe / Mn-ZSM-5 molecular sieve.

[0053] Example 4

[0054] This embodiment describes a method for preparing Fe / Mn-ZSM-5 molecular sieves based on Fischer-Tropsch synthesis waste. The method is essentially the same as in Example 1, and the preparation steps are briefly described below:

[0055] S1: The Fischer-Tropsch synthesis waste residue is heated to 350°C in a muffle furnace and roasted for 30 minutes, then removed for later use.

[0056] S2: Mass ratio:

[0057] The mixture of n(SiO2):n(Al2O3):n(Fe2O3):n(Mn(NO3)2):n(Na2O):n(H2O):n(TPABr) = 1:0.01:0.01:0.01:0.2:30:0.2 was prepared. Pretreated Fischer-Tropsch synthesis waste, sodium hydroxide, silicon source, manganese source, water, and tetrapropylammonium bromide were added, mixed, and stirred until homogeneous. The solid-liquid mixture was poured into a polytetrafluoroethylene liner and subjected to hydrothermal reaction in a stainless steel reactor. Crystallization was carried out at 180°C for 24 hours. After cooling, filtration, and washing, the mixture was dried at 105°C for 5 hours.

[0058] S3: Finally, the dried sample was calcined in a muffle furnace at 550℃ for 5 hours to remove the template agent and obtain Fe / Mn-ZSM-5 molecular sieve.

[0059] Example 5

[0060] This embodiment describes a method for preparing Fe / Mn-ZSM-5 molecular sieves based on Fischer-Tropsch synthesis waste. The method is essentially the same as in Example 1, and the preparation steps are briefly described below:

[0061] S1: The Fischer-Tropsch synthesis waste residue is heated to 350°C in a muffle furnace and roasted for 30 minutes, then removed for later use.

[0062] S2: Mass ratio:

[0063] The mixture of n(SiO2):n(Al2O3):n(Fe2O3):n(Mn(NO3)2):n(Na2O):n(H2O):n(TPABr) = 1:0.01:0.01:0.01:0.08:30:0.2 was prepared. Pretreated Fischer-Tropsch synthesis waste, sodium hydroxide, silicon source, manganese source, water, and tetrapropylammonium bromide were added, mixed, and stirred until homogeneous. This solid-liquid mixture was poured into a polytetrafluoroethylene liner and subjected to hydrothermal reaction in a stainless steel reactor. Crystallization was carried out at 180°C for 24 hours. After cooling, filtration, and washing, the mixture was dried at 105°C for 5 hours.

[0064] S3: Finally, the dried sample was calcined in a muffle furnace at 550℃ for 5 hours to remove the template agent and obtain Fe / Mn-ZSM-5 molecular sieve.

[0065] Example 6

[0066] This embodiment describes a method for preparing Fe / Mn-ZSM-5 molecular sieves based on Fischer-Tropsch synthesis waste. The method is essentially the same as in Example 1, and the preparation steps are briefly described below:

[0067] S1: The Fischer-Tropsch synthesis waste residue is heated to 350°C in a muffle furnace and roasted for 30 minutes, then removed for later use.

[0068] S2: Mass ratio:

[0069] The formula is: n(SiO2):n(Al2O3):n(Fe2O3):n(Mn(NO3)2):n(Na2O):n(H2O):n(TPABr) = 1:0.01:0.01:0.01:0.1:30:0.2. Pretreated Fischer-Tropsch synthesis waste, sodium hydroxide, silicon source, manganese source, water, and tetrapropylammonium bromide are added, mixed, and stirred until homogeneous. This solid-liquid mixture is poured into a polytetrafluoroethylene liner and subjected to hydrothermal reaction in a stainless steel reactor. The crystallization process conditions are: crystallization at 170℃ for 24 hours. After cooling, filtration, and washing, the mixture is dried at 105℃ for 5 hours.

[0070] S3: Finally, the dried sample was calcined in a muffle furnace at 550℃ for 5 hours to remove the template agent and obtain Fe / Mn-ZSM-5 molecular sieve.

[0071] Example 7

[0072] This embodiment describes a method for preparing Fe / Mn-ZSM-5 molecular sieves based on Fischer-Tropsch synthesis waste. The method is essentially the same as in Example 1, and the preparation steps are briefly described below:

[0073] S1: The Fischer-Tropsch synthesis waste residue is heated to 350°C in a muffle furnace and roasted for 30 minutes, then removed for later use.

[0074] S2: Mass ratio:

[0075] The formula is: n(SiO2):n(Al2O3):n(Fe2O3):n(Mn(NO3)2):n(Na2O):n(H2O):n(TPABr) = 1:0.01:0.01:0.01:0.1:30:0.2. Pretreated Fischer-Tropsch synthesis waste, sodium hydroxide, silicon source, manganese source, water, and tetrapropylammonium bromide are added, mixed, and stirred until homogeneous. This solid-liquid mixture is poured into a polytetrafluoroethylene liner and subjected to a hydrothermal reaction in a stainless steel reactor. The crystallization process conditions are: crystallization at 190℃ for 24 hours. After cooling, filtration, and washing, the mixture is dried at 105℃ for 5 hours.

[0076] S3: Finally, the dried sample was calcined in a muffle furnace at 550℃ for 5 hours to remove the template agent and obtain Fe / Mn-ZSM-5 molecular sieve.

[0077] The degradation experiment of Rhodamine B in water by the Fe / Mn-ZSM-5 molecular sieve obtained in this invention was conducted. The Fe / Mn-ZSM-5 molecular sieve prepared in Example 1 was used as a catalyst to degrade and remove Rhodamine B from aqueous solution by catalytic H2O2. The specific steps were as follows: 50 ml of a 10 mg / L Rhodamine B solution was prepared in a 100 ml beaker, 15 mg of catalyst was added, and then 20 mmol / L H2O2 was added. The mixture was stirred in a magnetic stirrer at 25°C. 5 mL of the solution was centrifuged at different times, and the absorbance of the supernatant was measured at 554 nm using a UV-Vis spectrophotometer. Finally, the concentration of Rhodamine B was calculated using a calibration curve.

[0078] The catalytic degradation effect is shown in Figure 3. After 60 min of reaction, the removal rate of Rhodamine B by H2O2 catalyzed by Fe / Mn-ZSM-5 molecular sieve reached 98.21%. This indicates that the Fe / Mn-ZSM-5 molecular sieve prepared in this invention exhibits good catalytic activity for the degradation of Rhodamine B. The Fe2p and Mn2p spectra of the Fe / Mn-ZSM-5 molecular sieve are shown in Figure 4 and Figure 5. Figure 5 After adsorption and oxidation reactions, the peak area ratio of Fe(III) / Fe(II) increased, while the peak area ratio of Mn(III) / Mn(II) decreased. This indicates that some Fe(II) and Mn(III) in the used Fe / Mn-ZSM-5 molecular sieve were converted into Fe(III) and Mn(II), suggesting a redox cycle between Mn(II) / Mn(III) and Fe(II) / Fe(III) species, which promotes the catalytic reaction.

[0079] The above description is a further detailed explanation of the present invention in conjunction with specific preferred embodiments. It should not be considered that the specific embodiments of the present invention are limited to this. For those skilled in the art, several simple deductions or substitutions can be made without departing from the present invention, and all of these should be considered to fall within the scope of patent protection determined by the submitted claims.

Claims

1. A method for preparing Fe / Mn-ZSM-5 type molecular sieve based on waste residue of Fischer-Tropsch synthesis, characterized in that, The application relates to a preparation method of Fe / Mn-ZSM-5 type molecular sieve. 1) A waste residue of a Fischer-Tropsch synthesis is pretreated by roasting to remove organic components and is prepared; the roasting temperature of the waste residue of the Fischer-Tropsch synthesis is 300-400 DEG C, and the roasting time is 25-35 min; 2) A silicon source, an aluminum source and an iron source are provided by using the waste residue of the Fischer-Tropsch synthesis; a pretreated waste residue of the Fischer-Tropsch synthesis, sodium hydroxide, a silicon source, a manganese source, water and a template agent are added according to a molar ratio of n (SiO2): n (Al2O3): n (Fe2O3): n (Mn (NO3)2): n (Na2O): n (H2O): n (TPABr) = 1:0.01:0.01:0.01:0.1:30:0.2, are uniformly mixed and stirred, and then are poured into a reaction kettle to perform a crystallization reaction; after water washing and drying, the template agent is removed by roasting to obtain the Fe / Mn-ZSM-5 type molecular sieve. The Fe / Mn-ZSM-5 type molecular sieve is used for heterogeneous Fenton catalytic degradation of waste water containing rhodamine B.

2. The method for preparing Fe / Mn-ZSM-5 type molecular sieve based on waste residue of Fischer-Tropsch synthesis according to claim 1, characterized in that, The silicon source is silica sol.

3. The method for preparing Fe / Mn-ZSM-5 type molecular sieve based on waste residue of Fischer-Tropsch synthesis according to claim 1, characterized in that, The manganese source is manganese nitrate.

4. The method for preparing Fe / Mn-ZSM-5 type molecular sieve based on waste residue of Fischer-Tropsch synthesis according to claim 1, characterized in that, The template agent is tetrapropylammonium bromide.

5. The method for preparing Fe / Mn-ZSM-5 type molecular sieve based on waste residue of Fischer-Tropsch synthesis according to claim 1, characterized in that, The temperature of the crystallization reaction is 170-190 DEG C, and the crystallization time is 20-28 h.

6. The method for preparing Fe / Mn-ZSM-5 type molecular sieve based on waste residue of Fischer-Tropsch synthesis according to claim 1, characterized in that, The temperature of the drying is 100-120 DEG C, and the drying time is 4-6 h.

7. The method for preparing Fe / Mn-ZSM-5 type molecular sieve based on waste residue of Fischer-Tropsch synthesis according to claim 1, characterized in that, The temperature of the roasting to remove the template agent is 500-600 DEG C, and the roasting time is 4-6 h.

8. The method for preparing Fe / Mn-ZSM-5 type molecular sieve based on waste residue of Fischer-Tropsch synthesis according to claim 1, characterized in that, The reaction kettle is a stainless steel reaction kettle with a polytetrafluoroethylene lining.

Images