MN modified HZSM-5 molecular sieve catalyst for promoting desorption of CO2 pregnant solution as well as preparation method and application of MN modified HZSM-5 molecular sieve catalyst

Abstract

The invention provides an MN modified HZSM-5 molecular sieve catalyst for promoting desorption of a CO2 rich solution as well as a preparation method and application of the MN modified HZSM-5 molecular sieve catalyst, and belongs to the technical field of industrial catalysis. The molecular sieve catalyst comprises an HZSM-5 molecular sieve carrier and MnOx coated on the HZSM-5 molecular sieve carrier. The molecular sieve catalyst for promoting desorption of the ethanolamine (MEA) rich solution, provided by the invention, is simple in component, has more acid sites, is beneficial to promoting desorption of the rich solution, and can improve the desorption amount and the desorption rate of the MEA rich solution, reduce the desorption temperature and further reduce the energy consumption in the desorption process.

Description

Technical Field

[0001] The invention belongs to the technical field of industrial catalysis and specifically relates to a method for promoting CO 2 Rich liquid desorption MN modified HZSM-5 molecular sieve catalyst and its preparation method and application. Background Art

[0002] In the context of current global climate change, carbon dioxide (CO 2 ) emissions have become a focus of worldwide attention. Carbon dioxide capture and storage (CCS) is a technology to control CO 2 Chemical absorption is one of the most effective means of CO2 emission reduction, among which chemical absorption is the most promising method for industrial application. 2 However, the high investment cost and high operating energy consumption of chemical absorption method hinder the large-scale application of this technology. How to reduce the cost and operating energy consumption has become a current research hotspot.

[0003] In CO 2 The addition of molecular sieve catalysts during the desorption process has become one of the most promising carbon capture technologies, which can significantly increase CO 2 Desorption rate, increase CO 2 Desorption efficiency, reducing regeneration time and lowering regeneration temperature, thereby reducing regeneration energy consumption. Most of the molecular sieve catalysts proposed so far are composite catalysts formed by multiple components, such as Fe and PO 4 3- Loaded on molecular sieve catalyst, nano metal oxide Fe 2 O 3 and ZrO 2 Such catalysts are used for C0-rich 2 When in solution, although the desorption rate is improved, the desorption temperature is still high, and this type of catalyst requires a multi-component composite, the components are complex, and the preparation process is cumbersome. Summary of the invention

[0004] The present invention aims to solve at least one of the technical problems existing in the prior art and provide a method for promoting CO 2 MN modified HZSM-5 molecular sieve catalyst for rich liquid desorption, preparation method and application.

[0005] In one aspect of the present invention, there is provided a method for promoting CO 2 A molecular sieve catalyst for rich liquid desorption, the molecular sieve catalyst comprising: a HZSM-5 molecular sieve carrier, and MnO coated on the HZSM-5 molecular sieve carrier x .

[0006] Optionally, the MnO x Mn 2O 3 , MnO and MnO 2 .

[0007] Optionally, the MnO x The content is 10-13wt% of the molecular sieve catalyst.

[0008] Optionally, the molecular sieve catalyst has weak acid sites, medium acid sites and strong acid sites; wherein,

[0009] The acid strength of the weak acid site is 0.70-0.8 mmol / g, the acid strength of the medium acid site is 0.2-0.3 mmol / g, and the acid strength of the strong acid site is 0.15-0.25 mmol / g.

[0010] Optionally, the molecular sieve catalyst has Acid sites and Lewis acid sites; among them,

[0011] Said The acid strength of the acid site is 11-12 μmol / g, and the acid strength of the Lewis acid site is 71-72 μmol / g.

[0012] Another aspect of the present disclosure provides a method for preparing the molecular sieve catalyst described above, the method comprising:

[0013] Soak the HZSM-5 spherical particles in a manganese nitrate solution for 20-25 hours;

[0014] The impregnated HZSM-5 spherical particles are dried and calcined to obtain MnO x / HZSM-5 catalyst.

[0015] Optionally, the mass fraction of the manganese nitrate solution is 40-60wt%.

[0016] Optionally, during the soaking of the HZSM-5 spherical particles in the manganese nitrate solution, an ultrasonic vibrator is used to vibrate the particles for 25 to 35 minutes every 2.5 to 3.5 hours.

[0017] Optionally, the drying process is carried out at a temperature of 70-90° C. for a time of 10-14 h; and / or,

[0018] The calcination treatment is carried out at a temperature of 500-600°C and for a time of 4-6 hours.

[0019] In another aspect of the present disclosure, an application of a MN modified HZSM-5 molecular sieve catalyst is proposed, wherein the MN modified HZSM-5 molecular sieve catalyst described above is applied to promote CO 2 Rich liquid is being desorbed.

[0020] Optionally, the MN modified HZSM-5 molecular sieve catalyst is used to promote CO 2 The temperature of rich liquid desorption is 60-80℃.

[0021] The present invention proposes a method for promoting CO 2 MN modified HZSM-5 molecular sieve catalyst for rich liquid desorption, preparation method and application. The MN modified HZSM-5 molecular sieve catalyst comprises: a HZSM-5 molecular sieve carrier, and MnO coated on the HZSM-5 molecular sieve carrier. x The molecular sieve catalyst for promoting the desorption of ethanolamine (MEA) rich solution proposed by the present invention has simple components. The HZSM-5 molecular sieve carrier is modified by using Mn to load MnO on the HZSM-5 molecular sieve carrier. x , we get MnO x / HZSM-5 molecular sieve catalyst, which has more acid sites, is conducive to promoting the desorption of rich liquid, can increase the desorption amount and desorption rate of MEA rich liquid, reduce the desorption temperature, and thus reduce the energy consumption of the desorption process. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 It is a flowchart of a method for preparing a MN modified HZSM-5 molecular sieve catalyst in a specific embodiment of the present invention;

[0023] Figure 2 The MnO synthesized by the impregnation method in Example 1 of the present invention x / HZ catalyst process flow diagram;

[0024] Figure 3 This is a schematic diagram of a device for simulating the actual desorption of rich liquid CO2 in Example 1 of the present invention;

[0025] Figure 4 MnO of Example 1 of the present invention x / HZ catalyst SEM image and EDS image; Among them, Figure 4 (A) is a SEM image; Figure 4 (B) is the EDS spectrum of Al element. Figure 4 (C) is the EDS spectrum of Si element. Figure 4 (D) in the figure is the EDS spectrum of O element. Figure 4 (E) in the figure is the EDS spectrum of Mn element;

[0026] Figure 5 MnO of Example 1 of the present invention x / Mn 2p XPS spectrum of HZ catalyst;

[0027] Figure 6 MnO of Example 1 of the present inventionx , HZSM-5 and MnO x / XRD pattern of HZ catalyst;

[0028] Figure 7 MnO of Example 1 of the present invention x , HZSM-5 and MnO x NH / HZ catalyst 3 -TPD spectrum;

[0029] Figure 8 MnO of Example 1 of the present invention x , HZSM-5 and MnO x Py-IR spectrum of / HZ catalyst;

[0030] Fig. 9 The MEA rich solution after adding HZSM-5 molecular sieve, Mn-modified HZSM-5 molecular sieve and blank MEA rich solution CO in Example 1 of the present invention are shown in FIG. 2 Desorption rate results. DETAILED DESCRIPTION

[0031] In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention is further described in detail below in conjunction with the accompanying drawings and specific implementation methods. It should be understood that the specific embodiments described herein are only used to explain the present invention and are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work are within the scope of protection of the present invention.

[0032] In one aspect of the present invention, there is provided a method for promoting CO 2 A MN modified HZSM-5 molecular sieve catalyst for rich liquid desorption, the molecular sieve catalyst comprising: a HZSM-5 molecular sieve carrier, and MnO coated on the HZSM-5 molecular sieve carrier x .

[0033] In this embodiment, a single component of Mn is used to modify the HZSM molecular sieve, MnO x Loaded on HZSM-5 molecular sieve carrier to form MnO x / HZSM-5 molecular sieve catalyst, compared with catalysts loaded with other types of oxides, has more acid sites, which helps to promote faster desorption of CO by organic amine absorbent 2 , and at the same time can reduce the desorption temperature, thereby reducing the energy consumption of carbon capture.

[0034] It should be understood that, based on the porous structure of the HZSM-5 molecular sieve carrier, MnO xIt is not only loaded on the surface of the HZSM-5 molecular sieve carrier, but also loaded in the porous structure of the HZSM-5 molecular sieve carrier.

[0035] In some preferred embodiments, MnO x Mn 2 O 3 , MnO and MnO 2 , among which, MnO x Mainly Mn 2 O 3 It also exists in the form of MnO and MnO 2 It exists in the form of precipitates, which promotes the desorption effect of the rich liquid.

[0036] In other preferred embodiments, MnO x The content of MnO x / 10-13wt% of HZSM-5 molecular sieve catalyst, larger MnO x The loading amount can make the catalyst have sufficient catalytic performance.

[0037] It should also be understood that based on the Mn-modified HZSM-5 molecular sieve carrier, MnO x The / HZSM-5 catalyst has more acid sites, for example, weak acid sites, medium acid sites and strong acid sites.

[0038] In some preferred embodiments, the acid strength of the weak acid site is 0.70-0.8 mmol / g, the acid strength of the medium acid site is 0.2-0.3 mmol / g, the acid strength of the strong acid site is 0.15-0.25 mmol / g, and the total acid strength is 1.1-1.3 mmol / g.

[0039] In other preferred embodiments, the molecular sieve catalyst has Acid sites and Lewis acid sites. Among them, The acid strength of the acid site is 11-12 μmol / g, and the acid strength of the Lewis acid site is 71-72 μmol / g.

[0040] In this embodiment, when the modified molecular sieve catalyst is added to the organic amine absorbent, the CO desorption rate can be increased at a lower desorption temperature (e.g., 60°C-80°C). 2 desorption rate, thereby reducing CO 2 Sensible and latent heat of desorption process.

[0041] like Figure 1 As shown, another aspect of the present invention provides a method for promoting CO 2 The molecular sieve catalyst S100 for desorption of rich liquid specifically comprises the following steps S110 to S120:

[0042] S110, soak the HZSM-5 spherical particles in a manganese nitrate solution for 20-25 hours.

[0043] Specifically, combined with Figure 2 The spherical HZSM-5 is immersed in a 40-60wt% manganese nitrate solution at room temperature for 20-30 hours, and an ultrasonic oscillator is used to oscillate the solution for 25-35 minutes every 2.5-3.5 hours during the immersion process.

[0044] In some preferred embodiments, the mass fraction of the manganese nitrate solution is preferably 40wt%, 50wt%, 60wt%, etc.

[0045] In other preferred embodiments, the soaking time is preferably 20 h, 22 h, 24 h, 26 h, 28 h, 30 h, etc., and during the soaking process, an ultrasonic oscillator is preferably used to oscillate for 30 minutes every 3 hours.

[0046] S120, drying and calcining the impregnated HZSM-5 spherical particles to obtain MnO x / HZSM-5 catalyst.

[0047] Specifically, combined with Figure 2 The manganese nitrate solution remaining in step S110 is discarded, and the impregnated HZSM-5 spherical particles are dried at 70-90°C for 10-14h. Subsequently, the sample is placed in a muffle furnace, heated to 550°C at a heating rate of 5°C / min in an air environment, and calcined at 550°C for 5 hours. The sample prepared through the above steps is recorded as MnO x / HZ catalyst. According to the mass change of the sample after impregnation, the MnO in the catalyst was determined. x The mass fraction is about 10-13wt%.

[0048] In this embodiment, since the HZSM-5 spherical particles are loaded with a single component of MnO x , the MnO x The main components are Mn 2 O 3 There are also MnO and MnO 2 The prepared molecular sieve catalyst has multiple acid sites, which can promote CO 2 Rich liquid desorption helps to lower the desorption temperature and increase the desorption rate.

[0049] In another aspect of the present disclosure, an application of a MN modified HZSM-5 molecular sieve catalyst is proposed, wherein the MN modified HZSM-5 molecular sieve catalyst described above is applied to promote CO2 Rich liquid is being desorbed.

[0050] Specifically, combined with Figure 3 The prepared molecular sieve catalyst was used to simulate the actual rich liquid CO 2 In the desorption device, the device is mainly composed of a continuous stirring reactor, a mass flow controller, a constant temperature water bath, an online CO 2 Gas analyzer, peristaltic pump and N 2 During the experiment, a certain amount of MEA solution was added to the continuous stirring reactor, and the molecular sieve catalyst prepared above was added at the same time. The mass fraction of the molecular sieve catalyst in the MEA solution was 1.25wt%. The MEA rich solution with the added catalyst was stirred with a stirring paddle and heated from 30°C to 80°C. During the heating process, the desorbed CO 2 With N 2 The carrier gas is mixed with CO at the outlet 2 Gas analyzer monitoring, online estimation of CO 2 Desorption rate.

[0051] Furthermore, the following formula was used to estimate CO 2 Desorption rate:

[0052] The outlet CO of the continuous stirred reactor 2 The concentration can be derived from formula (1):

[0053]

[0054] in, (%) is CO 2 CO measured by the analyzer 2 concentration,

[0055] (mol·min -1 ) is the CO of MEA rich solution 2 Molar desorption rate, is a constant 0.04 mol·min -1 N 2 Flow rate.

[0056] therefore, It can be obtained from formula (2):

[0057]

[0058] The preparation method and specific application of MN modified HZSM-5 molecular sieve catalyst will be further described below in conjunction with specific examples:

[0059] Example 1

[0060] The preparation method of the molecular sieve catalyst in this example includes the following steps: Figure 2 As shown:

[0061] S1. Soak the spherical HZSM-5 in a 50 wt% manganese nitrate solution at room temperature for 24 hours, and use an ultrasonic oscillator to vibrate for 30 minutes every 3 hours during the soaking process.

[0062] S2, pour out the residual manganese nitrate solution in step S1, and dry the impregnated spherical particles at 80°C for 12 hours. Then, put the sample into a muffle furnace, heat it to 550°C at a heating rate of 5°C / min in an air environment, and calcine it at 550°C for 5 hours. Through the above steps, the prepared sample is recorded as MnO x / HZ catalyst, recorded as sample 1.

[0063] Furthermore, in Example 1, the prepared MnO x / HZ catalysts were characterized, MnO x / HZ catalyst surface Al, O, Si, Mn elements and their distribution Figure 4 The results show that the Mn element is uniformly doped into the HZSM-5 molecular sieve. x MnO in HZ catalyst x The valence state and mass fraction of Mn were measured by XPS and ICP-OES, respectively. The results are as follows Figure 5 XPS results show that in MnO x In the HZ catalyst, Mn 3+ is the main valence state, Mn 2+ and Mn 4 + is a minor valence state, indicating that MnO x Mainly Mn 2 O 3 There are also MnO and MnO 2 Therefore, the mass fraction of Mn determined by ICP-OES can be used to estimate the MnO x The mass fraction of MnO is shown in Table 1. The results of XPS and ICP-OES show that x / MnO in HZSM-5 x The mass fraction is 10.6wt%, which is consistent with the mass change results before and after immersion.

[0064] Furthermore, in this embodiment 1, MnO x The structural characteristics of the MnO / HZ catalyst were compared with those of the unmodified HZSM-5 catalyst, as shown in Table 2. xThe specific surface area and pore volume of the HZ / HZ catalyst decreased slightly.

[0065] Furthermore, XRD was used to characterize the HZSM-5, MnO x and MnO x / HZ catalysts were characterized respectively, and the results are shown in Figure 6 The characteristic diffraction peaks at 23.1° and 23.9° are attributed to HZSM-5, and the characteristic diffraction peaks at 32.8°, 38.2°, 55.3° and 65.8° are attributed to MnO x According to MnO x The XRD pattern of / HZ confirms that MnO x was successfully loaded on HZSM-5, and MnO x / HZ corresponding to HZSM-5 characteristic peak intensity weakened, indicating that MnO x The loading of has an inhibitory effect on the crystallinity of HZSM-5.

[0066] Furthermore, using NH 3 -TPD was used to determine HZSM-5 and MnO x / HZ and MnO x The acidity is as follows Figure 7 As shown in Table 3, it can be found that HZSM-5 and MnO x NH / HZ 3 The desorption curve has an obvious peak near 100℃, which is caused by the weak acid of the catalyst. The peaks at 300-550℃ and above 550℃ belong to the medium and strong acid sites. As listed in Table 3, MnO x The modification of MnO x HZ has more acid sites than HZSM-5, so MnO is loaded on HZSM-5. x Can effectively enhance its acidity.

[0067] Furthermore, in order to determine the type of acid sites on the catalyst surface, this Example 1 also separately x / HZ catalyst, HZSM-5 and MnO x Py-IR characterization was performed. x / HZ and MnO x The Py-IR results are as follows Figure 8 As shown in Table 4, at 1450, 1490, 1540 and 1610 cm -1 Strong bands were observed at 1450 and 1610 cm -1 Belongs to the Lewis acid site, 1540cm -1 belong Acid sites. As can be seen from Table 4, MnO x / HZ The acid sites, Lewis acid sites and total acid sites are 11.09 μmol / g, 71.11 μmol / g and 82.2 μmol / g respectively, which are all higher than those of HZSM-5. This is due to the fact that MnO x Mainly Lewis acid catalyst, its modification of HZSM-5 can introduce more acid sites into MnO x / HZ, which is different from NH 3 -TPD results were consistent.

[0068] Furthermore, refer to Figure 3 As shown, the prepared MnO x / HZ catalyst for rich liquid CO 2 In the desorption device, during the experiment, 400 mL of 5 M MEA solution was added to the continuous stirred reactor. 2 The loading is 0.5 molCO 2 / mol MEA, and 5g MnO x / HZ catalyst 1, MnO x The mass fraction of / HZ catalyst 1 in the MEA solution was 1.25wt%. The MEA rich solution with and without catalyst / filler was stirred with a stirring paddle (100rpm) and heated from 30°C to 80°C. During the heating process, the desorbed CO 2 With N 2 The carrier gas is mixed with CO at the outlet 2 Gas analyzer monitoring, online estimation of CO 2 Desorption rate.

[0069] It should be noted that in Example 1, a continuous stirred reactor was used to test blank MEA rich solution and MEA rich solution with or without the addition of catalyst (e.g., HZSM-5 and MnO x / HZ) under the conditions of CO 2 The desorption rate is as follows Fig. 9 When the temperature is lower than 59°C, the CO 2 The desorption rate is less than 0.1×10 -2 mol·min -1 However, when the rich solution temperature is higher than 59°C, CO 2 The desorption rate varies with the filler used. CO of MEA rich liquid without catalyst / filler and MEA rich liquid with HZSM-5 catalyst 2 The peak desorption rates are 0.7×10 -2 mol·min -1 and 0.9×10 -2 mol·min-1 Adding MnO x / HZ catalyst, CO in rich liquid 2 The peak desorption rate can reach 1.31×10 -2 mol·min -1 , compared with the CO of the rich liquid without adding catalyst / filler 2 The desorption rate increased by 87% compared to the CO in the HZSM-5-rich solution. 2 The desorption rate increased by 45.6%. In addition, it can be found that when MnO is added at 69 °C, x / HZ catalyst MEA rich liquid CO 2 Desorption rate vs. rich liquid CO without catalyst / filler at 78°C 2 The desorption rate is close. This indicates that the addition of MnO x / HZ catalyst can reduce CO 2 desorption temperature, thereby reducing CO 2 Sensible and latent heat of desorption process.

[0070] Example 2

[0071] The preparation method of the molecular sieve catalyst in this example includes the following steps:

[0072] S1. Soak the spherical HZSM-5 in a 50 wt% manganese nitrate solution at room temperature for 24 hours, and use an ultrasonic oscillator to vibrate for 30 minutes every 3 hours during the soaking process.

[0073] S2, pour out the residual manganese nitrate solution in step S1, and dry the impregnated spherical particles at 80°C for 12 hours. Then, put the sample into a muffle furnace, heat it to 550°C at a heating rate of 5°C / min in an air environment, and calcine it at 550°C for 5 hours. Through the above steps, the prepared sample is recorded as MnO x / HZ catalyst, recorded as sample 2.

[0074] As shown in Table 1, according to the mass change of sample 2 after impregnation, MnO x The mass fraction is about 12.6wt%.

[0075] Example 3

[0076] The preparation method of the molecular sieve catalyst in this example includes the following steps:

[0077] S1. Soak the spherical HZSM-5 in a 50 wt% manganese nitrate solution at room temperature for 24 hours, and use an ultrasonic oscillator to vibrate for 30 minutes every 3 hours during the soaking process.

[0078] S2, pour out the residual manganese nitrate solution in step S1, and dry the impregnated spherical particles at 80°C for 12 hours. Then, put the sample into a muffle furnace, heat it to 550°C at a heating rate of 5°C / min in an air environment, and calcine it at 550°C for 5 hours. Through the above steps, the prepared sample is recorded as MnO x / HZ catalyst, recorded as sample 3.

[0079] As shown in Table 1, according to the mass change of sample 3 after impregnation, MnO x The mass fraction is about 11.5wt%.

[0080] Table 1 Mass fraction of Mn and Mn oxide in different examples

[0081]

[0082] Table 2 Structural characteristics of different catalysts in Example 1

[0083]

[0084] Table 3 Acid strength of different catalysts in Example 1

[0085]

[0086] Table 4 Acid types of different catalysts in Example 1

[0087]

[0088] In summary, according to Examples 1-3, when the mass fraction of the precursor solution is 50wt%, the immersion time is 24h, the drying is performed at 80℃ for 12h, and the calcination is performed at 550℃ for 5h, MnO x / HZSM-5 catalyst, and the MnO x / HZSM-5 catalyst, MnO x The mass fraction is between 10-13wt%, the loading amount is high, and it has more acid sites, which is beneficial to promote the desorption of the rich solution.

[0089] The present invention proposes a method for promoting CO 2 The MN modified HZSM-5 molecular sieve catalyst for rich liquid desorption and its preparation method and application have the following beneficial effects compared with the prior art: the components of the molecular sieve catalyst are simple, and the MnO x The components and mass fraction of MEA rich liquid can significantly increase the desorption amount and desorption rate, while reducing the desorption temperature and the energy consumption of the desorption process, thereby reducing the chemical absorption method for capturing CO 2 cost.

[0090] It is to be understood that the above embodiments are merely exemplary embodiments used to illustrate the principles of the present invention, but the present invention is not limited thereto. For those of ordinary skill in the art, various modifications and improvements can be made without departing from the spirit and essence of the present invention, and these modifications and improvements are also considered to be within the scope of protection of the present invention.

Claims

1. A MN modified HZSM-5 molecular sieve catalyst for promoting desorption of CO2 rich liquid, characterized in that: The MN modified HZSM-5 molecular sieve catalyst comprises: a HZSM-5 molecular sieve carrier, and MnO coated on the HZSM-5 molecular sieve carrier. x .

2. The MN modified HZSM-5 molecular sieve catalyst for promoting desorption of CO2 rich liquid according to claim 1, characterized in that: The MnO x It is Mn2O3, MnO and MnO2.

3. The MN modified HZSM-5 molecular sieve catalyst for promoting desorption of CO2 rich liquid according to claim 1, characterized in that: The MnO x The content is 10-13wt% of the molecular sieve catalyst.

4. The MN modified HZSM-5 molecular sieve catalyst for promoting desorption of CO2 rich liquid according to claim 1, characterized in that: The molecular sieve catalyst has weak acid sites, medium acid sites and strong acid sites; wherein, The acid strength of the weak acid site is 0.70-0.8 mmol / g, the acid strength of the medium acid site is 0.2-0.3 mmol / g, and the acid strength of the strong acid site is 0.15-0.25 mmol / g.

5. The MN modified HZSM-5 molecular sieve catalyst for promoting desorption of CO2 rich liquid according to claim 1, characterized in that: The molecular sieve catalyst has Acid sites and Lewis acid sites; among them, Said The acid strength of the acid site is 11-12 μmol / g, and the acid strength of the Lewis acid site is 71-72 μmol / g.

6. A method for preparing the MN modified HZSM-5 molecular sieve catalyst according to any one of claims 1 to 5, characterized in that: The method comprises: Soak the HZSM-5 spherical particles in a manganese nitrate solution for 20-25 hours; The impregnated HZSM-5 spherical particles are dried and calcined to obtain MnO x / HZSM-5 catalyst.

7. The method according to claim 6, characterized in that The mass fraction of the manganese nitrate solution is 40-60wt%.

8. The method according to claim 6, characterized in that During the soaking of the HZSM-5 spherical particles in the manganese nitrate solution, an ultrasonic vibrator is used to vibrate the particles for 25 to 35 minutes every 2.5 to 3.5 hours; and / or, The drying process is performed at a temperature of 70-90°C for a period of 10-14 hours; and / or, The calcination treatment is carried out at a temperature of 500-600°C and for a time of 4-6 hours.

9. An application of a MN modified HZSM-5 molecular sieve catalyst, characterized in that: The MN modified HZSM-5 molecular sieve catalyst described in any one of claims 1 to 5 is used to promote the desorption of CO2 rich liquid.

10. The use according to claim 9, characterized in that: The temperature at which the MN modified HZSM-5 molecular sieve catalyst is used to promote the desorption of CO2 rich liquid is 60-80°C.

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