CN109485063B - Method for preparing Y molecular sieve from waste MTP catalyst and application of waste MTP catalyst - Google Patents
Method for preparing Y molecular sieve from waste MTP catalyst and application of waste MTP catalyst Download PDFInfo
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Abstract
The invention discloses a method for preparing a Y molecular sieve by using a waste MTP catalyst, which comprises the following steps: (1) crushing the waste MTP catalyst into fine powder, mixing the fine powder of the waste MTP catalyst with alkali liquor with the concentration of 1-5mol/L according to the mass ratio of 1:5-20, and uniformly stirring to obtain slurry; (2) adding a proper amount of guiding agent and water into the slurry obtained in the step (1), uniformly stirring to obtain a suspension, and then transferring the suspension into a hydrothermal kettle for crystallization; (3) and after crystallization, cooling, washing, drying and roasting the crystallized product to obtain the final product. According to the method, the waste MTP catalyst is used as a raw material, a silicon source and an aluminum source do not need to be additionally added, the Y molecular sieve can be effectively synthesized by adopting the process conditions for synthesizing the Y molecular sieve, waste materials are changed into valuable materials, resources are saved, the waste MTP catalyst is converted into the Y molecular sieve with high added value, and the method has very important social significance and economic value.
Description
Technical Field
The invention belongs to the field of catalyst preparation, relates to a method for recycling a waste MTP catalyst, and particularly relates to a method for preparing a Y molecular sieve by using the waste MTP catalyst and application of the waste MTP catalyst.
Background
Low carbon olefins, especially ethylene and propylene, are leading products of petrochemical products and are one of the important marks for measuring the development degree of the national petrochemical industry and economy. Ethylene is mainly used for producing polyethylene, the prepared polyethylene is widely applied to agricultural films, adhesives, wires and cables, packaging and polymer processing propylene is mainly used for producing polypropylene, acetone, butanol, octanol, phenol, synthetic glycerin and the like, and the prepared polypropylene is widely applied to daily necessities such as plastic products, film products, fiber products and the like.
The existing olefin production methods can be generally divided into two categories, one is a petroleum route, the other is a technology for preparing synthesis gas by taking natural gas or coal as a raw material, and the synthesis gas is subjected to Fischer-Tropsch synthesis or low-carbon olefin preparation through methanol or dimethyl ether. Among them, the process of preparing low-carbon olefins such as ethylene and propylene from methanol, i.e. the MTP process, using coal or natural gas as a raw material is considered to be a very attractive and promising route for replacing naphtha cracking to prepare low-carbon olefins. The energy structure of China is characterized by rich coal, poor oil and little gas, and in the total amount of fossil energy, 95.6 percent of the fossil energy is coal, 3.2 percent of the fossil energy is petroleum, and 1.2 percent of the fossil energy is natural gas. Therefore, in terms of the comparison of reserves of coal and petroleum in China, the low-carbon olefin is prepared by using the coal as the raw material and adopting the MTP process, so that the resources can be more reasonably and effectively utilized, the current situation of shortage of petroleum resources is favorably alleviated, and the requirements of chemical raw materials in a long time in the future can be met.
The MTP catalyst used in the MTP process is mainly a ZSM-5 molecular sieve active component containing silicon and aluminum species. With the popularization of MTP processes, a large amount of deactivated spent MTP catalyst is generated. At present, the waste MTP catalyst can be regenerated by roasting → acid leaching → water washing → activation → drying, or treated by direct landfill. The regeneration process is complicated, and the activity of the MTP catalyst is reduced; direct landfill not only results in a great deal of waste of silicon and aluminum species, but also occupies a great deal of land resources.
Therefore, there is an urgent need for an efficient method for the rational resource recycling of existing spent MTP catalysts.
Disclosure of Invention
The Y molecular sieve can be used as an active component of a catalytic cracking catalyst, is an important molecular sieve, and has important influence on the catalytic cracking process in terms of production process, performance and production cost. Researchers have conducted long-term studies on the synthesis process of Y molecular sieves for many years. At present, no technology for directly synthesizing the Y molecular sieve by using the waste MTP catalyst exists. The first purpose of the invention is to provide a method for preparing a Y molecular sieve by using a waste MTP catalyst, so as to reasonably recycle the resources of the existing waste MTP catalyst.
The technical scheme of the invention is as follows:
the method for preparing the Y molecular sieve by using the waste MTP catalyst comprises the following preparation steps:
(1) crushing the waste MTP catalyst into fine powder, mixing the fine powder of the waste MTP catalyst with alkali liquor with the concentration of 1-5mol/L according to the mass ratio of 1:5-20, and uniformly stirring to obtain slurry;
(2) adding a proper amount of guiding agent and water into the slurry obtained in the step (1), uniformly stirring to obtain a suspension, and then transferring the suspension into a hydrothermal kettle for crystallization;
(3) and after crystallization, cooling, washing, drying and roasting the crystallized product to obtain the final product.
In the step (2), the mass ratio of the slurry to the guiding agent to the water is (20-40) to 1 (25-50);
the guiding agent consists of Al2O3Calculated NaAlO2With SiO2Calculated by the mol ratio of water glass, NaOH and water to Al2O3:SiO2:NaOH:H2O is 1, (8-15), (10-15), (150) -300).
In the step (1), the carbon deposit is removed by roasting the waste MTP catalyst or the fine powder of the waste MTP catalyst; or the waste MTP catalyst fine powder can achieve the purpose of preparing the Y molecular sieve without roasting.
The slurry contains active silicon and active aluminum which are necessary for synthesizing the Y molecular sieve.
The crystallization adopts the conventional crystallization conditions for preparing the Y molecular sieve in the prior art.
According to the invention, in the step (1), the waste MTP catalyst or the waste MTP catalyst fine powder is roasted to remove carbon deposition, and then is mixed with alkali liquor.
According to the invention, in the step (1), the mixing and stirring temperature is controlled to be 50-90 ℃, and the stirring time is 1-5 h.
According to the invention, in the step (1), the alkali liquor is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate solution.
According to the invention, in the step (2), the crystallization temperature is controlled to be 90-150 ℃, and the crystallization time is 10-24 h.
Preferably, in the step (2), the crystallization temperature is controlled to be 120-.
According to the invention, in the step (3), the roasting temperature of the crystallized product is controlled to be 500-700 ℃, and the roasting time is controlled to be 3-10 hours.
According to the invention, the silicon/aluminum molar ratio of the waste MTP catalyst is 2-7, and the coking rate is 4-15%.
Preferably, the coke rate of the waste MTP catalyst is 6-15%.
Further preferably, the coke rate of the waste MTP catalyst is 10-15%.
The second purpose of the invention is to provide an application of the waste MTP catalyst for preparing the Y molecular sieve. According to the invention, the waste MTP catalyst is used for preparing the Y molecular sieve, a silicon source and an aluminum source do not need to be additionally added, the obtained Y molecular sieve meets the industrial application requirements, and the method is economical and environment-friendly and can effectively realize the recycling of the waste MTP catalyst.
According to the application, the waste MTP catalyst is used for preparing the hierarchical porous Y molecular sieve, and the specific surface area of micropores of the prepared Y molecular sieve is 400-700m2Per g, external specific surface area of 30-250m2/g。
The waste MTP catalyst is used for preparing the hierarchical pore Y molecular sieve, a silicon source and an aluminum source do not need to be additionally added, the obtained hierarchical pore Y molecular sieve meets the requirement of industrial application, has a large micropore surface area, a large external specific surface area and hierarchical pores, the application of the hierarchical pore Y molecular sieve in the field of catalysis or adsorption is remarkably expanded, a decoking process is not needed, the steps are simplified, and the production cost is saved.
Compared with the prior art, the invention has the following beneficial technical effects:
1) according to the method for preparing the Y molecular sieve by using the waste MTP catalyst, the waste MTP catalyst is prepared into the Y molecular sieve and the hierarchical-pore Y molecular sieve by using the characteristic that the silica-alumina ratio of the waste MTP catalyst is basically close to that of the ultrastable Y molecular sieve and no additional silicon source or aluminum source is needed, so that the waste MTP catalyst is changed into the Y molecular sieve with high added value, the waste is changed into valuable, the resources are saved, and the method has very important social significance and economic value.
2) The waste MTP catalyst contains green coke, and the Y molecular sieve prepared by directly using the green coke as a hard template has multi-stage pores, rich pore channel structures, larger micropore specific surface area and external specific surface area, expands the application of the Y molecular sieve in the field of catalysis or adsorption, does not need a decoking process, simplifies the steps, and saves the production cost.
Drawings
FIG. 1 is a comparison of XRD patterns for Y molecular sieve samples A-I prepared in examples 1-9, and for a commercial Y molecular sieve standard J.
Wherein the abscissa represents the 2 θ angle and the ordinate represents the characteristic peak intensity.
Detailed Description
The present invention will be further described with reference to the following examples. It should be understood that the following examples are illustrative only and are not intended to limit the scope of the present invention.
In the following examples, the waste MTP catalyst is a deactivated catalyst generated by MTP process, and the waste MTP catalyst is obtained from Dandotorn coal chemical company, and the detected silicon/aluminum molar ratio is 2-7, and the silicon/aluminum molar ratio is defined as SiO2With Al2O3The coke rate is 4-15%. According to different MTP process conditions, the coke rate of the waste MTP catalyst is different.
In the following examples, the spent MTP catalyst was crushed to a fine powder having a particle size of less than 10 microns.
The specific surface area of micropores of a commercially available Y molecular sieve standard J is measured to be 458m2Per g, external specific surface area of 12m2The XRD diffraction curve of the crystal is shown as a curve J in figure 1. The typical micropore specific surface area of the commercially available Y molecular sieve is 400-500m2Per g, external specific surface area of 1-20m2/g。
In all the following examples, XRD diffraction experimental conditions of the final products A-I are the same as those of the Y molecular sieve standard J. The BET specific surface area measuring method and conditions of the final product A-I are the same as those of the Y molecular sieve standard J.
EXAMPLE 1 preparation of Y molecular sieves from spent MTP catalyst
In this example, the spent MTP catalyst had a Si/Al molar ratio of 2 and a coke formation of 4%. The method for preparing the Y molecular sieve by using the waste MTP catalyst comprises the following steps:
(1) adding 40g of waste MTP catalyst fine powder into 200g of 5mol/L sodium hydroxide solution, and stirring for 3 hours at the temperature of 50 ℃ to obtain slurry;
(2) adding 12g of guiding agent and 300g of water into the slurry obtained in the step (1), stirring for 1h to obtain a suspension, then transferring the suspension into a hydrothermal kettle for crystallization, controlling the crystallization temperature to be 90 ℃ and the crystallization time to be 10h, and obtaining a crystallization product after crystallization is finished;
(3) and (3) cooling and washing the crystallized product obtained in the step (2) to be neutral, drying to obtain powder, and roasting the powder at 500 ℃ for 10 hours to obtain the final product.
Wherein: in the step (2), the guiding agent is composed of Al2O3Calculated NaAlO2With SiO2Calculated by the mol ratio of water glass, NaOH and water to Al2O3:SiO2:NaOH:H2O1: 9:10:200 at 30 deg.C, the material amount is NaAlO28.33g, water glass 88g, NaOH 3.9g and water 83 g.
An XRD spectrogram of the product obtained in step (3) is detected by an XRD diffraction method, as shown in a curve a in fig. 1, comparing the curve a with a curve J of a commercially available Y molecular sieve standard, it can be known that the characteristic diffraction peak of the product prepared in this example belongs to the characteristic diffraction peak corresponding to the Y molecular sieve, and the product prepared in this example is the Y molecular sieve.
The specific surface area of micropores of the product obtained in the step (3) was measured by the BET method to be 452m2(g) an external specific surface area of 123m2It can be seen that the Y molecular sieve prepared in this example has hierarchical pores, has rich pore structure, and has a large specific micropore surface area and a large external specific surface area.
Example 2 preparation of Y molecular sieves from spent MTP catalyst
In this example, the spent MTP catalyst had a Si/Al molar ratio of 2 and a coke formation of 4%. The method for preparing the Y molecular sieve by using the waste MTP catalyst comprises the following steps:
(1) adding 40g of waste MTP catalyst fine powder into 200g of 1mol/L sodium hydroxide solution, and stirring for 3 hours at the temperature of 50 ℃ to obtain slurry;
(2) adding 12g of guiding agent and 300g of water into the slurry obtained in the step (1), stirring for 1h to obtain a suspension, then transferring the suspension into a hydrothermal kettle for crystallization, controlling the crystallization temperature to be 90 ℃ and the crystallization time to be 10h, and obtaining a crystallization product after crystallization is finished;
(3) and (3) cooling and washing the crystallized product obtained in the step (2) to be neutral, drying to obtain powder, and roasting the powder at 600 ℃ for 5 hours to obtain the final product.
Wherein: in the step (2), the guiding agent is composed of Al2O3Calculated NaAlO2With SiO2Calculated by the mol ratio of water glass, NaOH and water to Al2O3:SiO2:NaOH:H2O1: 8:12:300 at 30 deg.C, the material amount is NaAlO28.33g, water glass 78g, NaOH 8.3g and water 162 g.
An XRD spectrogram of the product obtained in step (3) is detected by an XRD diffraction method, as shown in a curve B in fig. 1, comparing a curve a with a curve J of a commercially available Y molecular sieve standard, it can be known that the characteristic diffraction peak of the product prepared in this example is attributed to the characteristic diffraction peak corresponding to the Y molecular sieve, and the product prepared in this example is the Y molecular sieve.
The specific surface area of micropores of the product obtained in the step (3) was measured by the BET method to be 500m2Per g, external specific surface area of 135m2It can be seen that the Y molecular sieve prepared in this example has hierarchical pores, has rich pore structure, and has a large specific micropore surface area and a large external specific surface area.
Example 3 preparation of Y molecular sieves from spent MTP catalyst
In this example, the spent MTP catalyst had a Si/Al molar ratio of 3 and a coke formation of 6%. The method for preparing the Y molecular sieve by using the waste MTP catalyst comprises the following steps:
(1) adding 40g of waste MTP catalyst fine powder into 800g of 1mol/L sodium hydroxide solution, and stirring for 2 hours at the temperature of 60 ℃ to obtain slurry;
(2) adding 24g of guiding agent and 600g of water into the slurry obtained in the step (1), stirring for 1h to obtain a suspension, then transferring the suspension into a hydrothermal kettle for crystallization, controlling the crystallization temperature at 150 ℃ and the crystallization time at 15h, and obtaining a crystallization product after crystallization is finished;
(3) and (3) cooling and washing the crystallized product obtained in the step (2) to be neutral, drying to obtain powder, and roasting the powder at 500 ℃ for 3 hours to obtain the final product.
Wherein, in the step (2), the guiding agent is made of Al2O3Calculated NaAlO2With SiO2Calculated by the mol ratio of water glass, NaOH and water to Al2O3:SiO2:NaOH:H2O1: 10:11:250, respectively, and NaAlO at 30 deg.C28.33g, water glass 98g, NaOH 4.6g and water 112 g.
An XRD spectrogram of the product obtained in step (3) is detected by an XRD diffraction method, as shown in curve C in fig. 1, comparing curve C with curve J of a commercially available Y molecular sieve standard, it can be known that the characteristic diffraction peak of the product prepared in this example belongs to the characteristic diffraction peak corresponding to the Y molecular sieve, and the product prepared in this example is the Y molecular sieve.
The specific surface area of micropores of the product obtained in the step (3) was determined by the BET method to be 565m2G, external specific surface area of 162m2It can be seen that the Y molecular sieve prepared in this example has hierarchical pores, has rich pore structure, and has a large specific micropore surface area and a large external specific surface area.
Example 4 preparation of Y molecular sieves from spent MTP catalyst
In this example, the spent MTP catalyst had a Si/Al molar ratio of 4 and a coke formation of 10%. The method for preparing the Y molecular sieve by using the waste MTP catalyst comprises the following steps:
(1) adding 40g of waste MTP catalyst fine powder into 200g of 1mol/L sodium carbonate solution, and stirring for 2 hours at the temperature of 60 ℃ to obtain slurry;
(2) adding 12g of guiding agent and 600g of water into the slurry obtained in the step (1), stirring for 1h to obtain a suspension, then transferring the suspension into a hydrothermal kettle for crystallization, controlling the crystallization temperature to be 120 ℃ and the crystallization time to be 10h, and obtaining a crystallization product after crystallization is finished;
(3) and (3) cooling and washing the crystallized product obtained in the step (2) to be neutral, drying to obtain powder, and roasting the powder at 650 ℃ for 3 hours to obtain the final product.
Wherein: in the step (2), the guiding agent is composed of Al2O3Calculated NaAlO2With SiO2Calculated by the mol ratio of water glass, NaOH and water to Al2O3:SiO2:NaOH:H2O1: 15:15:280 at 30 deg.C, the material amount is NaAlO28.33g, water glass 147g, NaOH 6.6g and water 100 g.
An XRD spectrogram of the product obtained in step (3) is detected by an XRD diffraction method, as shown in a curve D in fig. 1, comparing the curve D with a curve J of a commercially available Y molecular sieve standard, it can be known that the characteristic diffraction peak of the product prepared in this example belongs to the characteristic diffraction peak corresponding to the Y molecular sieve, and the product prepared in this example is the Y molecular sieve.
The specific surface area of micropores of the product obtained in the step (3) was measured by the BET method to be 610m2Per g, external specific surface area of 180m2It can be seen that the Y molecular sieve prepared in this example has hierarchical pores, has rich pore structure, and has a large specific micropore surface area and a large external specific surface area.
Example 5 preparation of Y molecular sieves from spent MTP catalyst
In this example, the spent MTP catalyst had a Si/Al molar ratio of 6 and a coke formation of 15%. The method for preparing the Y molecular sieve by using the waste MTP catalyst comprises the following steps:
(1) adding 50g of waste MTP catalyst fine powder into 250g of 1mol/L potassium carbonate solution, and stirring for 2 hours at the temperature of 70 ℃ to obtain slurry;
(2) adding 10g of guiding agent and 400g of water into the slurry obtained in the step (1), stirring for 1h to obtain a suspension, then transferring the suspension into a hydrothermal kettle for crystallization, controlling the crystallization temperature to be 120 ℃ and the crystallization time to be 10h, and obtaining a crystallization product after crystallization is finished;
(3) and (3) cooling and washing the crystallized product obtained in the step (2) to be neutral, drying to obtain powder, and roasting the powder at 500 ℃ for 7 hours to obtain the final product.
Wherein: in the step (2), the guiding agent is composed of Al2O3Calculated NaAlO2With SiO2Calculated by the mol ratio of water glass, NaOH and water to Al2O3:SiO2:NaOH:H2O1: 8:10:150 at 30 deg.C, the material amount is NaAlO28.33g, water glass 78g, NaOH 4.8g and water 54 g.
An XRD spectrogram of the product obtained in step (3) is detected by an XRD diffraction method, as shown in a curve E in fig. 1, comparing the curve E with a curve J of a commercially available Y molecular sieve standard, it can be known that the characteristic diffraction peak of the product prepared in this example belongs to the characteristic diffraction peak corresponding to the Y molecular sieve, and the product prepared in this example is the Y molecular sieve.
The micropore specific surface area of the product obtained in step (3) was found to be 645m by the BET method2G, external specific surface area of 238m2It can be seen that the Y molecular sieve prepared in this example has hierarchical pores, has rich pore structure, and has a large specific micropore surface area and a large external specific surface area.
EXAMPLE 6 preparation of Y molecular sieves from spent MTP catalyst
In this example, the spent MTP catalyst had a Si/Al molar ratio of 6 and a coke formation of 15%. The method for preparing the Y molecular sieve by using the waste MTP catalyst comprises the following steps:
(1) adding 50g of waste MTP catalyst fine powder into 500g of 4mol/L sodium hydroxide solution, and stirring for 1h at the temperature of 90 ℃ to obtain slurry;
(2) adding 13.75g of guiding agent and 687.5g of water into the slurry obtained in the step (1), stirring for 5 hours to obtain a suspension, then transferring the suspension into a hydrothermal kettle for crystallization, controlling the crystallization temperature to be 120 ℃ and the crystallization time to be 24 hours, and obtaining a crystallization product after crystallization is finished;
(3) and (3) cooling and washing the crystallized product obtained in the step (2) to be neutral, drying to obtain powder, and roasting the powder at 700 ℃ for 3 hours to obtain the final product.
Wherein: in the step (2), the guiding agent is composed of Al2O3Calculated NaAlO2With SiO2Calculated by the mol ratio of water glass, NaOH and water to Al2O3:SiO2:NaOH:H2Mixing O1: 12:13:200 at 30 deg.C, and adding NaAlO28.33g, 118g of water glass, 6.0g of NaOH and 62.5g of water.
An XRD spectrogram of the product obtained in step (3) is detected by an XRD diffraction method, as shown in fig. 1, comparing curve F with curve J of a commercially available Y molecular sieve standard, it can be known that the characteristic diffraction peak of the product prepared in this example belongs to the characteristic diffraction peak corresponding to the Y molecular sieve, and the product prepared in this example is the Y molecular sieve.
The specific surface area of micropores of the product obtained in the step (3) was 534m as determined by the BET method2Per g, external specific surface area 149m2It can be seen that the Y molecular sieve prepared in this example has hierarchical pores, has rich pore structure, and has a large specific micropore surface area and a large external specific surface area.
Example 7 preparation of Y molecular sieves from spent MTP catalyst
In this example, the spent MTP catalyst had a Si/Al molar ratio of 7 and a coke formation of 15%. The method for preparing the Y molecular sieve by using the waste MTP catalyst comprises the following steps:
(1) adding 50g of waste MTP catalyst fine powder into 500g of 4mol/L potassium hydroxide solution, and stirring for 5 hours at the temperature of 50 ℃ to obtain slurry;
(2) adding 13.75g of guiding agent and 687.5g of water into the slurry obtained in the step (1), stirring for 5 hours to obtain a suspension, then transferring the suspension into a hydrothermal kettle for crystallization, controlling the crystallization temperature to be 120 ℃ and the crystallization time to be 24 hours, and obtaining a crystallization product after crystallization is finished;
(3) and (3) cooling and washing the crystallized product obtained in the step (2) to be neutral, drying to obtain powder, and roasting the powder at 700 ℃ for 3 hours to obtain the final product.
Wherein: in the step (2), the guiding agent is composed of Al2O3Calculated NaAlO2With SiO2Calculated by the mol ratio of water glass, NaOH and water to Al2O3:SiO2:NaOH:H2O1: 11:14:180 at 30 ℃ and the feed amount is divided intoOther than NaAlO28.33g, 108g of water glass, 8.6g of NaOH and 55g of water.
An XRD spectrogram of the product obtained in step (3) is detected by an XRD diffraction method, as shown in a curve G in fig. 1, comparing the curve G with a commercially available Y molecular sieve standard, it can be known that the characteristic diffraction peak of the product prepared in this example belongs to the characteristic diffraction peak corresponding to the Y molecular sieve, and the product prepared in this example is the Y molecular sieve.
The specific surface area of the micropores of the product obtained in the step (3) was 545m as determined by the BET method2(g) an external specific surface area of 145m2It can be seen that the Y molecular sieve prepared in this example has hierarchical pores, has rich pore structure, and has a large specific micropore surface area and a large external specific surface area.
As can be seen from the comparative curve of FIG. 1, the diffraction peaks of the final products prepared in examples 1-7 are consistent with the characteristic diffraction peak of the Y molecular sieve, indicating that the invention can synthesize pure phase Y molecular sieve from the waste MTP catalyst. In addition, in the examples 1-7, the hierarchical pore Y molecular sieve can be prepared, and the specific surface area of the micropores is 452-2(g) external specific surface area of 123-2/g。
The specific surface area of the micropores and the external specific surface area can be changed within a certain range according to different actual operating conditions, and the specific surface area of the micropores is 400-700m2Per g, external specific surface area of 30-250m2(ii) in terms of/g. By adopting the methods of embodiments 1 to 7, the Y molecular sieve can be prepared from the waste MTP catalyst without additionally adding a silicon source and an aluminum source, and the recycling of the waste MTP catalyst can be effectively realized.
EXAMPLE 8 preparation of Y molecular sieves from spent MTP catalyst
In this example, the spent MTP catalyst had a Si/Al molar ratio of 2 and a coke formation of 4%. The method for preparing the Y molecular sieve by using the waste MTP catalyst comprises the following steps:
(1) and roasting the waste MTP catalyst for 4 hours at 600 ℃ in the air atmosphere to remove carbon deposition, crushing the waste MTP catalyst into waste MTP catalyst fine powder, adding 40g of the waste MTP catalyst fine powder into 200g of 5mol/L sodium hydroxide solution, and stirring for 3 hours at 50 ℃ to obtain slurry.
(2) Adding 12g of guiding agent and 300g of water into the slurry obtained in the step (1), stirring for 1h to obtain a suspension, then transferring the suspension into a hydrothermal kettle for crystallization, controlling the crystallization temperature to be 90 ℃ and the crystallization time to be 10h, and obtaining a crystallization product after crystallization is finished.
(3) And (3) cooling and washing the crystallized product obtained in the step (2) to be neutral, drying to obtain powder, and roasting the powder at 500 ℃ for 6 hours to obtain the final product.
Wherein: in the step (2), the guiding agent is composed of Al2O3Calculated NaAlO2With SiO2Calculated by the mol ratio of water glass, NaOH and water to Al2O3:SiO2:NaOH:H2O1: 9:10:200 at 30 deg.C, the material amount is NaAlO28.33g, water glass 88g, NaOH 3.9g and water 83 g.
An XRD spectrogram of the final product obtained in step (3) is detected by an XRD diffraction method, as shown in curve H in fig. 1, comparing curve H with curve J of a commercially available Y molecular sieve standard, it can be known that the characteristic diffraction peak of the product prepared in this example belongs to the characteristic diffraction peak corresponding to the Y molecular sieve, and the product prepared in this example is the Y molecular sieve.
The final product obtained in the step (3) has a specific surface area of 465m in micropores as measured by the BET method2Per g, external specific surface area of 18m2It can be seen from this that the Y molecular sieve prepared in this example has a large specific surface area of micropores.
EXAMPLE 9 preparation of Y molecular sieves from spent MTP catalyst
In this example, the spent MTP catalyst had a Si/Al molar ratio of 7 and a coke formation of 15%. The method for preparing the Y molecular sieve by using the waste MTP catalyst comprises the following steps:
(1) and taking 50g of waste MTP catalyst fine powder, roasting for 4 hours at 600 ℃ in the air atmosphere, removing carbon deposition, then adding the carbon deposition into 500g of 4mol/L potassium hydroxide solution, and stirring for 5 hours at 50 ℃ to obtain slurry.
(2) Adding 13.75g of guiding agent and 687.5g of water into the slurry obtained in the step (1), stirring for 5 hours to obtain a suspension, then transferring the suspension into a hydrothermal kettle for crystallization, controlling the crystallization temperature to be 120 ℃ and the crystallization time to be 24 hours, and obtaining a crystallization product after crystallization.
(3) And (3) cooling and washing the crystallized product obtained in the step (2) to be neutral, drying to obtain powder, and roasting the powder at 700 ℃ for 3 hours to obtain the final product.
Wherein: in the step (2), the guiding agent is composed of Al2O3Calculated NaAlO2With SiO2Calculated by the mol ratio of water glass, NaOH and water to Al2O3:SiO2:NaOH:H2O ═ 1:11:14:180 was prepared by mixing at 30 ℃.
An XRD spectrogram of the final product obtained in step (3) is detected by an XRD diffraction method, as shown in curve I in fig. 1, comparing curve I with curve J of a commercially available Y molecular sieve standard, it can be known that the characteristic diffraction peak of the product prepared in this example belongs to the characteristic diffraction peak corresponding to the Y molecular sieve, and the product prepared in this example is the Y molecular sieve.
The final product obtained in step (3) was measured by the BET method to have a specific surface area of 530m in micropores2Per g, external specific surface area of 16m2It can be further seen that the Y molecular sieve prepared in this example has a large specific surface area of micropores.
As can be seen from the comparative curve in fig. 1, the diffraction peaks of the final products prepared in examples 8 and 9 conform to the characteristic diffraction peak of the Y molecular sieve, which indicates that examples 8 and 9 can also synthesize a pure-phase Y molecular sieve from the waste MTP catalyst, and the waste MTP catalyst can be effectively recycled without adding additional silicon source and aluminum source. And the Y molecular sieve can be prepared in the examples 8 and 9, and the specific surface area of the micropores of the Y molecular sieve is in the range of the specific surface area of the standard substance of the Y molecular sieve.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications or alterations to this practice will occur to those skilled in the art and are intended to be within the scope of this invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.
Claims (8)
1. The method for preparing the Y molecular sieve by using the waste MTP catalyst is characterized by comprising the following preparation steps of:
(1) crushing the waste MTP catalyst into fine powder, mixing the fine powder of the waste MTP catalyst with alkali liquor with the concentration of 1-5mol/L according to the mass ratio of 1:5-20, and uniformly stirring to obtain slurry;
(2) adding a proper amount of guiding agent and water into the slurry obtained in the step (1), uniformly stirring to obtain a suspension, and then transferring the suspension into a hydrothermal kettle for crystallization;
(3) after crystallization, cooling, washing, drying and roasting the crystallized product to obtain a final product;
in the step (2), the mass ratio of the slurry to the guiding agent to the water is (20-40) to 1 (25-50);
the guiding agent consists of Al2O3Calculated NaAlO2With SiO2Calculated by the mol ratio of water glass, NaOH and water to Al2O3:SiO2:NaOH:H2O is 1 (8-15) and 10-15 (150-300);
the waste MTP catalyst or the waste MTP catalyst fine powder is not subjected to roasting.
2. The method for preparing a Y molecular sieve by using the waste MTP catalyst according to claim 1, wherein in the step (1), the mixing and stirring temperature is controlled to be 50-90 ℃, and the stirring time is 1-5 h.
3. The method for preparing a Y molecular sieve with the waste MTP catalyst according to claim 1, wherein in the step (1), the alkali solution is one or more selected from sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate solution.
4. The method for preparing the Y molecular sieve by using the waste MTP catalyst according to claim 1, wherein in the step (2), the crystallization temperature is controlled to be 90-150 ℃ and the crystallization time is controlled to be 10-24 h.
5. The method for preparing Y molecular sieve with waste MTP catalyst as claimed in claim 1, wherein in the step (3), the calcination temperature of the crystallized product is controlled to be 500-700 ℃, and the calcination time is controlled to be 3-10 hours.
6. The method for preparing Y molecular sieve with waste MTP catalyst according to claim 1, wherein the waste MTP catalyst has a Si/Al molar ratio of 2-7 and a coking rate of 4-15%.
7. The method for preparing Y molecular sieve with waste MTP catalyst according to claim 6, wherein the coke rate of the waste MTP catalyst is 6-15%.
8. The application of the waste MTP catalyst is characterized in that the waste MTP catalyst is used for preparing a hierarchical pore Y molecular sieve, and the specific surface area of micropores of the Y molecular sieve is 400-700m2Per g, external specific surface area of 30-250m2/g。
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| CN114632544B (en) * | 2022-02-22 | 2024-05-24 | 中科合成油技术股份有限公司 | Catalyst for preparing olefin by coupling naphtha with low-carbon alcohol ether, and preparation method and application thereof |
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