CN114890434B - Mesoporous-enriched SAPO-34 molecular sieve prepared from MTO (methyl thiazolyl tetrazolium) spent catalyst and preparation method thereof - Google Patents
Mesoporous-enriched SAPO-34 molecular sieve prepared from MTO (methyl thiazolyl tetrazolium) spent catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention provides a mesoporous-enriched SAPO-34 molecular sieve prepared by using an MTO waste catalyst and a preparation method thereof. The preparation method comprises the following steps: roasting the waste MTO catalyst fine powder; mixing the calcined waste MTO catalyst fine powder with water and crushing the mixture by a shearing device to obtain a mixed solution; adding phosphoric acid into the mixed solution and stirring to obtain molecular sieve precursor gel; drying the molecular sieve precursor gel to obtain dry gel; grinding the dry glue into powder, mixing with an organic amine template agent, and crystallizing; and drying at least the crystallized product, and roasting to obtain the mesoporous-enriched SAPO-34 molecular sieve. The mesoporous size of the SAPO-34 molecular sieve rich in mesopores is 10-50nm. The invention uses MTO waste catalyst as raw material, does not need to add silicon source and aluminum source, has small template agent dosage and shorter crystallization time, and realizes the recycling of waste resources.
Description
Technical Field
The invention relates to a mesoporous-enriched SAPO-34 molecular sieve prepared by using an MTO (methyl thiazolyl tetrazolium) dead catalyst and a preparation method thereof, belonging to the technical field of preparation of molecular sieves.
Background
The methanol to olefins reaction is usually carried out in a circulating fluidized bed with continuous reaction-regeneration, which is determined by the technical characteristics possessed by MTO. The whole reaction process is carried out in gas (raw material gas and product gas) and solid (catalyst) phases, the gas phase is in a turbulent state, and the solid phase catalyst particles inevitably collide, agglomerate and the like and are subjected to mechanical abrasion. Eventually, the catalyst particles subjected to repeated attrition will fall into spent catalyst fines and no longer participate in the reaction because the particle size distribution does not meet fluidization requirements.
Unlike FCC spent catalysts containing heavy metals such as copper, nickel, vanadium, etc., the MTO spent catalyst of methanol feed is typically buried intensively, but the molecular sieves rich in silicon, aluminum, phosphorus sources are discarded and are also a waste of resources. The molecular sieve with high catalytic activity prepared by using the waste catalysts has wide application prospect, and CN111072046A discloses a method for preparing the ZSM-5 molecular sieve by using the catalytic cracking waste catalysts, thereby realizing the efficient recycling of the FCC waste catalysts.
To date, SAPO-34 molecular sieves remain the most interesting MTO catalysts. The research results of the charcoal burning regeneration dynamics model of the SAPO-34 molecular sieve catalyst with a plurality of deactivation modes show that the diffusion capacity of the molecular sieve is improved, and the inert carbon deposit generation which is easy to cause the rapid deactivation of the catalyst in the MTO reaction can be effectively inhibited. The introduction of the hierarchical pore structure is one of the ways to effectively enhance the mass transfer rate of the molecular sieve. The existing synthesis method of the hierarchical pore SAPO-34 is mainly concentrated on the aspects of top-down method, acid-base post-treatment, fluoride etching and the like. Direct crystallization has been the most desirable route to mesoporous-rich molecular sieves, but this has been difficult to break through due to the complexity and variety of synthetic gels.
In addition, the preparation method of the mesoporous SAPO-34 molecular sieve is still mainly based on traditional hydrothermal synthesis, and other methods such as xerogel conversion and the like are still rare.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide the mesoporous-enriched SAPO-34 molecular sieve prepared by using the MTO waste catalyst and a preparation method thereof. According to the preparation method disclosed by the invention, a xerogel conversion method is adopted, the mesoporous-rich SAPO-34 molecular sieve is prepared in a direct crystallization process, and the waste MTO catalyst fine powder is used as a synthesis raw material of the molecular sieve, so that a silicon source and an aluminum source are not required to be additionally added, the consumption of a template agent is small, the crystallization time is short, the synthesis route is environment-friendly, the synthesis cost of the molecular sieve can be reduced, and the recycling of waste resources can be realized.
In order to achieve the above objects, the present invention firstly provides a method for preparing a mesoporous-rich SAPO-34 molecular sieve using an MTO spent catalyst, comprising the steps of:
(1) Roasting the waste MTO catalyst fine powder;
(2) Mixing the calcined waste MTO catalyst fine powder with a certain amount of water, and crushing by using a shearing device to obtain a mixed solution;
(3) Adding phosphoric acid into the mixed solution obtained in the step (2), and stirring for a period of time at a certain temperature to obtain molecular sieve precursor gel;
(4) Drying the molecular sieve precursor gel obtained in the step (3) to obtain a dry gel;
(5) Grinding the dry glue obtained in the step (4) into powder, mixing the powder with an organic amine template agent, and crystallizing for a period of time;
(6) And drying at least the crystallized product, and roasting to obtain the mesoporous-enriched SAPO-34 molecular sieve.
In the above production method, preferably, the fresh catalyst corresponding to the waste MTO catalyst fine powder used in the step (1) is SAPO-34 molecular sieve, and the Si/Al molar ratio of the waste MTO catalyst fine powder is 1 (2-5) (more preferably 1 (3.5-4.5)). More preferably, the Si/Al/P molar ratio of the spent MTO catalyst fines is 1 (2-5): 1-2.5. It is particularly preferred that the Si/Al/P molar ratio of the spent MTO catalyst fines be 1:4:1.
In the above-mentioned production method, preferably, the waste MTO catalyst fine powder used in the step (1) is a completely deactivated waste MTO catalyst, and there is no characteristic diffraction peak of SAPO-34 molecular sieve in the X-ray diffraction pattern thereof. That is, the X-ray diffraction pattern of the used spent MTO catalyst fines showed no characteristic diffraction peaks of the SAPO-34 framework at 9.6 DEG, 12.8 DEG, 16.2 DEG, 21.5 DEG and 30.9 deg. More preferably, the complete deactivation of the spent MTO catalyst fines is accomplished by exposing the spent MTO catalyst fines that are not fully deactivated to air at room temperature for an extended period of time (at least 3 months). The waste MTO catalyst fine powder which is not completely deactivated is the waste MTO catalyst of the SAPO-34 molecular sieve which is eliminated in industry.
The invention creatively adopts the completely deactivated waste MTO catalyst to synthesize the SAPO-34 molecular sieve. The SAPO-34 framework in the completely deactivated waste MTO catalyst collapses, but a large amount of structural fragments such as a microcrystalline structure or a secondary structural unit of the SAPO-34 still exist, and the fragments are equivalent to providing a large amount of crystal nuclei in the crystallization process, so that the supersaturation concentration of the crystal nuclei in the mother liquor is increased, and the growth process of the crystals is slowed down, thereby synthesizing the molecular sieve with small granularity.
In the above preparation method, preferably, the baking temperature in the step (1) is 600 to 800 ℃ and the baking time is 6 to 8 hours. The invention calcines the waste MTO catalyst to remove carbon deposit.
In the above-mentioned production method, preferably, the mixing mass ratio of the calcined waste MTO catalyst fine powder in step (2) to water is 1: (1-5). Wherein, the water used in the step (2) can be deionized water.
In the above production method, preferably, the shearing device in the step (2) is a shearing emulsifying mixer, and the rotational speed at which the crushing is performed is 10000 to 28000rpm. More preferably, the time for crushing by the shearing device is 30min to 2 hours. The invention utilizes a shearing device to crush the calcined waste MTO catalyst fine powder so as to separate the binder and the filler in the waste catalyst fine powder.
In the above production method, preferably, the mass ratio of phosphoric acid added in step (3) to the calcined waste MTO catalyst fine powder in step (2) is 1: (0.3-2.5). More preferably, the phosphoric acid added is an aqueous solution of phosphoric acid having a mass concentration of 85%, and the mass ratio of the aqueous solution of phosphoric acid having a mass concentration of 85% added in step (3) to the calcined waste MTO catalyst fine powder in step (2) is 1: (0.3-2.5). It is particularly preferred that the mass ratio of the 85% aqueous phosphoric acid solution added in step (3) to the calcined waste MTO catalyst fine powder in step (2) is 1: (1.8-2.3).
In the above preparation method, preferably, in the step (3), phosphoric acid is added to the mixed solution obtained in the step (2), and stirred at 80-120 ℃ for 2-6 hours, thereby obtaining the molecular sieve precursor gel. More preferably, the stirring speed is 400-700r/min.
In the above preparation method, preferably, the pH value of the molecular sieve precursor gel obtained in the step (3) is 5 to 10. More preferably, the pH of the molecular sieve precursor gel obtained in step (3) is from 5 to 6. In the step (3) of the invention, a small amount of phosphoric acid is added into the mixed solution of the calcined waste MTO catalyst fine powder and water, thereby playing a role in regulating the pH value of the system.
In the above preparation method, preferably, the drying in the step (4) is performed at a temperature of 100 to 120 ℃ for a time of 4 to 12 hours.
In the above preparation method, preferably, the organic amine template in the step (5) includes one or a combination of several of diethylamine, triethylamine, morpholine, tetraethylammonium hydroxide, and the like.
In the above preparation method, preferably, the mixing mass ratio of the powder in step (5) to the organic amine template is 1: (0.2-1.5). More preferably, the mixing mass ratio of the powder in step (5) to the organic amine template is 1: (0.2-0.6).
In the above preparation method, preferably, the crystallization in the step (5) is carried out at a temperature of 180 to 220℃and a crystallization time of 2 to 10 hours (more preferably 2 to 6 hours). More preferably, the crystallization is performed in a stainless steel reactor with polytetrafluoroethylene lining at a constant temperature in a sealed manner. After crystallization is completed, the crystallized product can be naturally cooled to room temperature, and then the subsequent steps of separation, washing, drying and the like are carried out. Wherein the separation may be by centrifugation to separate out the solid product. The washing can be carried out by adopting deionized water, and the solid product obtained by separation is washed to be neutral. In addition, the present invention is not particularly limited in the order of separation and washing, and washing may be performed first and then separation may be performed, and separation may be performed after each washing. These may be conventional operations in the art.
In the above preparation method, preferably, the drying in step (6) is performed at a temperature of 100 to 120℃for a time of 4 to 12 hours.
In the above preparation method, preferably, the baking in step (6) is performed at a temperature of 500 to 700 ℃ for a time of 4 to 8 hours.
The invention also provides a mesoporous-enriched SAPO-34 molecular sieve prepared by the MTO waste catalyst, which is prepared by the preparation method.
According to a specific embodiment of the present invention, the average crystal size of the mesoporous enriched SAPO-34 molecular sieve is preferably 300 to 800nm, and the mesoporous size is 10 to 50nm, more preferably 10 to 30nm.
The SAPO-34 molecular sieve of the invention is rich in mesopores, which is mainly caused by etching defect parts in the synthetic crystal by a template agent in mother liquor. Because of the proportions of the raw materials defined in the invention and the fully deactivated waste MTO catalyst fine powder adopted, SAPO-34 crystals grow in an attached manner on smaller structural units, and meanwhile, the synthesis system is an aluminum-rich system, namely, the aluminum content is excessive, so that defects existing in the form of end groups are easy to generate in the growth process of the crystals. The defect parts with lower order degree are easy to be etched by mother liquor to be dissolved preferentially, namely, the template agent organic amine with strong alkalinity in the crystallization process is slowly released into the mother liquor to increase the pH value of the mother liquor, so that the inside of the SAPO-34 molecular sieve with a compact structure which grows well originally is dissolved preferentially, and a rich mesoporous structure is formed.
The invention uses MTO waste catalyst fine powder as raw material to prepare the SAPO-34 molecular sieve rich in mesopores, successfully realizes the resource utilization of MTO waste catalyst, reduces the pressure of dangerous waste treatment of related enterprises, and actively responds to the policy call of changing waste into valuable and recycling. The preparation method of the invention is a method for preparing the mesoporous SAPO-34 molecular sieve in the direct crystallization process, and compared with the traditional preparation method, the preparation method of the invention avoids the introduction of expensive template agent and also avoids the environmental pollution risk caused by acid-base aftertreatment. In addition, the preparation method adopts a xerogel conversion method, so that the phenomena of wall sticking and caking tendency frequently occurring in the traditional hydrothermal method synthesis are reduced; water is not needed as a mixing medium, so that a large amount of water resources are saved, a large amount of amine-containing wastewater is avoided, and the environment pollution is reduced. Meanwhile, the preparation method takes the waste MTO catalyst fine powder as the synthesis raw material of the molecular sieve, does not need to additionally add a silicon source and an aluminum source, has small template agent consumption and short crystallization time, has a green and environment-friendly synthesis route, reduces the synthesis cost of the molecular sieve, realizes the recycling of waste resources, and improves the resource utilization rate. The preparation method provided by the invention prepares the SAPO-34 molecular sieve rich in mesopores, and effectively improves the diffusion performance of the molecular sieve.
Drawings
FIG. 1 is an X-ray diffraction pattern of a sample of spent catalyst, fresh agent, and molecular sieve of examples 1-3.
Fig. 2a is a transmission electron micrograph of a molecular sieve sample of example 1.
Fig. 2b is a transmission electron micrograph of a molecular sieve sample of example 2.
Fig. 2c is a transmission electron micrograph of a molecular sieve sample of example 3.
FIG. 3 is N of molecular sieve samples of examples 1-3 2 Isothermal adsorption curve.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1
The embodiment provides a mesoporous-rich SAPO-34 molecular sieve prepared by using an MTO waste catalyst, and the preparation method comprises the following steps:
roasting the waste MTO catalyst fine powder at 600 ℃ for 6 hours to remove carbon deposit. 10g of waste MTO catalyst fine powder after roasting and removing carbon deposition is mixed with 30g of deionized water, and crushed for 30min by a shearing and emulsifying stirrer with the rotating speed of 10000rpm, so as to obtain a mixed solution. Adding 4.5g of 85% phosphoric acid aqueous solution into the mixed solution, uniformly stirring, heating in a water bath at 95 ℃ and stirring for 3 hours at the speed of 400-700r/min to obtain a gel precursor. The gel precursor was dried in an oven at 100 ℃ for 4 hours to give a dry gel. After the dry gel was ground into powder with a mortar, the mass of the powder was 10g, 2.4g of diethylamine was added, and after stirring uniformly, it was transferred to a stainless steel reaction kettle having a polytetrafluoroethylene liner for sealing, and crystallized in an oven at 180 ℃ for 2 hours. Washing the crystallized product with a large amount of deionized water after crystallization, and separating solid and liquid phases; after the pH value of the liquid phase system is 6-7, washing and centrifugation are finished, the solid phase product is transferred to a 110 ℃ oven for drying for 12 hours, and then baked for 6 hours at 550 ℃ to obtain a mesoporous-enriched SAPO-34 molecular sieve sample (named S1).
The XRD spectrum of the mesoporous-rich SAPO-34 molecular sieve sample (designated as S1) is shown in FIG. 1, and a Transmission Electron Microscope (TEM) photograph is shown in FIG. 2 a. The molecular sieve is a SAPO-34 molecular sieve with the CHA topological structure, and shows stronger characteristic diffraction peaks belonging to the SAPO-34 framework at 9.6 degrees, 12.8 degrees, 16.2 degrees, 21.5 degrees and 30.9 degrees, the molecular sieve is in a cubic morphology, the average crystal granularity is about 500nm, the inside of the SAPO-34 molecular sieve is rich in mesoporous structures, and the mesoporous size is 10-30nm.
In contrast, the XRD patterns of the used waste MTO catalyst fine powder, the fresh agent (which is the fresh agent corresponding to the used waste MTO catalyst fine powder in this example) are also shown in FIG. 1. Wherein, the waste MTO catalyst fine powder adopted is the waste MTO catalyst which is completely deactivated, and as shown in figure 1, the characteristic diffraction peak of the SAPO-34 molecular sieve does not exist in the X-ray diffraction pattern. That is, the characteristic diffraction peaks of the SAPO-34 framework are not exhibited at 9.6 °, 12.8 °, 16.2 °, 21.5 ° and 30.9 °. This example completely deactivated the spent MTO catalyst fines was achieved by exposing the spent MTO catalyst fines, which were not completely deactivated, to air at room temperature for a long period of time (3 months). The waste MTO catalyst fine powder which is not completely deactivated is the waste MTO catalyst of the SAPO-34 molecular sieve which is eliminated in industry. The molar Si/Al/P ratio of the spent MTO catalyst fines employed in this example was 1 (3.5-4.5): 1-2.5.
Example 2
The embodiment provides a mesoporous-rich SAPO-34 molecular sieve prepared by using an MTO waste catalyst, and the preparation method comprises the following steps:
the spent MTO catalyst fines (which are fully deactivated spent MTO catalyst fines as in example 1) were calcined at 650 ℃ for 8 hours to remove soot. 8g of waste MTO catalyst fine powder after roasting and removing carbon deposition is mixed with 15g of deionized water, and crushed for 1h by a shearing and emulsifying stirrer, wherein the rotating speed is 20000rpm, and a mixed solution is obtained. Adding 4g of 85% phosphoric acid aqueous solution into the mixed solution, uniformly stirring, heating in a water bath at 80 ℃ and stirring for 6 hours, wherein the stirring speed is 400-700r/min, and obtaining the gel precursor. The gel precursor was dried in an oven at 100 ℃ for 8 hours to give a dry gel. After the dry gel was ground into powder with a mortar, the mass of the powder was 8g, 3.6g of triethylamine was added, and after stirring uniformly, the powder was transferred to a stainless steel reaction kettle having a polytetrafluoroethylene liner for sealing, and crystallized in an oven at 200 ℃ for 3 hours. Washing the crystallized product with a large amount of deionized water after crystallization, and separating solid and liquid phases; after the pH value of the liquid phase system is 6-7, washing and centrifugation are finished, the solid phase product is transferred to a 110 ℃ oven for drying for 12 hours, and then baked for 8 hours at 550 ℃ to obtain a mesoporous-enriched SAPO-34 molecular sieve sample (named S2).
The XRD spectrum of the mesoporous-rich SAPO-34 molecular sieve sample (designated as S2) is shown in FIG. 1, and a Transmission Electron Microscope (TEM) photograph is shown in FIG. 2 b. The molecular sieve is a SAPO-34 molecular sieve with the CHA topological structure, and shows stronger characteristic diffraction peaks belonging to the SAPO-34 framework at 9.6 degrees, 12.8 degrees, 16.2 degrees, 21.5 degrees and 30.9 degrees, the molecular sieve is in a cubic morphology, the average crystal granularity is about 400nm, the inside of the SAPO-34 molecular sieve is rich in mesoporous structures, and the mesoporous size is 20-30nm.
Example 3
The embodiment provides a mesoporous-rich SAPO-34 molecular sieve prepared by using an MTO waste catalyst, and the preparation method comprises the following steps:
the spent MTO catalyst fines (which are fully deactivated spent MTO catalyst fines as in example 1) were calcined at 650 ℃ for 6 hours to remove soot. 6g of waste MTO catalyst fine powder after calcination and removal of carbon deposition is mixed with 10g of deionized water, and crushed for 30min by a shearing and emulsifying stirrer at the rotating speed of 28000rpm, so as to obtain a mixed solution. Adding 2.8g of 85% phosphoric acid aqueous solution into the mixed solution, uniformly stirring, heating in a water bath at 100 ℃ and stirring for 2 hours at the speed of 400-700r/min to obtain a gel precursor. The gel precursor was dried in an oven at 100 ℃ for 6 hours to give a dry gel. After the dry gel was ground into powder with a mortar, the mass of the powder was 6g, 4.5g of morpholine was added, and after stirring uniformly, the powder was transferred to a stainless steel reaction kettle with polytetrafluoroethylene lining for sealing, and crystallized in an oven at 220 ℃ for 5 hours. Washing the crystallized product with a large amount of deionized water after crystallization, and separating solid and liquid phases; after the pH value of the liquid phase system is 6-7, the centrifugation is finished, the solid phase product is transferred to a 110 ℃ oven for drying for 6 hours, and then baked for 4 hours at 600 ℃ to obtain a SAPO-34 molecular sieve sample (named S3) rich in mesopores.
The XRD spectrum of the mesoporous-rich SAPO-34 molecular sieve sample (designated as S3) is shown in FIG. 1, and a Transmission Electron Microscope (TEM) photograph is shown in FIG. 2 c. The molecular sieve is a SAPO-34 molecular sieve with the CHA topological structure, and shows stronger characteristic diffraction peaks belonging to the SAPO-34 framework at 9.6 degrees, 12.8 degrees, 16.2 degrees, 21.5 degrees and 30.9 degrees, the molecular sieve is in a cubic morphology, the average crystal granularity is 300-400nm, the inside of the SAPO-34 molecular sieve is rich in mesoporous structures, and the mesoporous size is 10-20nm.
Test case
The nitrogen physical adsorption and desorption test was performed on the spent catalyst, which is the completely deactivated spent MTO catalyst fines used in examples 1-3, the fresh agent, which is the fresh agent corresponding to the spent MTO catalyst fines used in examples 1-3, and the molecular sieve samples obtained in examples 1-3, and the results are shown in table 1.
TABLE 1
| Sample name | Specific surface area (m) 2 /g) | Micropore area (m) 2 /g) | External surface area (m) 2 /g) |
| Fresh agent | 208 | 166 | 42 |
| Spent catalyst | 35 | 18 | 17 |
| S1 | 434 | 405 | 29 |
| S2 | 445 | 418 | 27 |
| S3 | 472 | 440 | 32 |
From Table 1, it can be seen that the 3 molecular sieve samples of examples 1-3 of the present invention all have a relatively high outer surface area, demonstrating the existence of a mesoporous structure.
FIG. 3 is N of molecular sieve samples of examples 1-3 2 Isothermal adsorption curve. As shown in fig. 3, the molecular sieve samples of examples 1-3 exhibited typical hysteresis loops at pressures ranging from 0.4 to 0.9, demonstrating a mesoporous-rich structure.
Thus, it can be seen from the above Table 1 and FIGS. 2a, 2b, 2c and 3 that all of the examples of the present invention produce a mesoporous enriched SAPO-34 molecular sieve.
Claims (11)
1. A method for preparing a mesoporous-enriched SAPO-34 molecular sieve with MTO spent catalyst, comprising the steps of:
(1) Roasting the waste MTO catalyst fine powder;
(2) Mixing the calcined waste MTO catalyst fine powder with a certain amount of water, and crushing by using a shearing device to obtain a mixed solution;
(3) Adding phosphoric acid into the mixed solution obtained in the step (2), and stirring for a period of time at a certain temperature to obtain molecular sieve precursor gel;
(4) Drying the molecular sieve precursor gel obtained in the step (3) to obtain a dry gel;
(5) Grinding the dry glue obtained in the step (4) into powder, mixing the powder with an organic amine template agent, and crystallizing for a period of time;
(6) Drying at least the crystallized product, and roasting to obtain the mesoporous-enriched SAPO-34 molecular sieve;
wherein, the fresh catalyst corresponding to the waste MTO catalyst fine powder adopted in the step (1) is SAPO-34 molecular sieve; the waste MTO catalyst fine powder adopted in the step (1) is a completely deactivated waste MTO catalyst, and the characteristic diffraction peak of the SAPO-34 molecular sieve does not exist in an X-ray diffraction pattern; and the Si/Al/P molar ratio of the waste MTO catalyst fine powder adopted in the step (1) is 1 (2-5): 1-2.5;
the mixing mass ratio of the calcined waste MTO catalyst fine powder to water in the step (2) is 1: (1-5);
the mass ratio of the phosphoric acid added in the step (3) to the calcined waste MTO catalyst fines in the step (2) is 1: (0.3-2.5);
the mixing mass ratio of the powder in the step (5) to the organic amine template agent is 1: (0.2-1.5).
2. The method according to claim 1, wherein the firing in step (1) is at a temperature of 600-800 ℃ for a time of 6-8 hours.
3. The method of claim 1, wherein the shearing device in step (2) is a shear emulsifying mixer which breaks at a speed of 10000-28000rpm.
4. The method according to claim 1, wherein in the step (3), phosphoric acid is added to the mixed solution obtained in the step (2), and stirred at 80-120 ℃ for 2-6 hours to obtain the molecular sieve precursor gel.
5. The method of claim 1, wherein the molecular sieve precursor gel obtained in step (3) has a pH of 5 to 10.
6. The method of claim 1, wherein the drying in step (4) is at a temperature of 100-120 ℃ for a time of 4-12 hours.
7. The method of claim 1, wherein the organic amine templating agent in step (5) comprises one or a combination of several of diethylamine, triethylamine, morpholine and tetraethylammonium hydroxide.
8. The method according to claim 1, wherein the crystallization in step (5) is performed at a temperature of 180-220 ℃ for a crystallization time of 2-10h.
9. The method according to claim 1, wherein the firing in step (6) is performed at a temperature of 500-700 ℃ for a time of 4-8 hours.
10. A mesoporous enriched SAPO-34 molecular sieve prepared with MTO spent catalyst, prepared by the method of any one of claims 1 to 9.
11. The mesoporous-rich SAPO-34 molecular sieve as claimed in claim 10, wherein the average crystal size of the mesoporous-rich SAPO-34 molecular sieve is 300 to 800nm and the mesoporous size is 10 to 50nm.
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