CN110451519B - Eutectic material containing MTW structure and preparation method thereof - Google Patents
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Abstract
The invention provides a eutectic material containing an MTW structure and a preparation method thereof, wherein the eutectic material comprises 1.2 to 98 mass percent of MTW structure material, and the balance of BEA or MOR structure material; the Si/Al atomic ratio in the eutectic material is 1-6000. The method can overcome the technical problem that the MTW/MOR eutectic molecular sieve and the MTW/BEA eutectic molecular sieve cannot be provided in the prior art, and the product variety is single by mixing the raw materials containing silicon element, aluminum element, water, organic molecules and the like under the condition that the pH value is more than 7, crystallizing the mixed materials at 120-200 ℃ for 20-200 hours, and separating the product to obtain the eutectic material containing the MTW structure.
Description
Technical Field
The invention relates to the technical field of molecular sieve materials, in particular to a eutectic material containing an MTW structure and a preparation method thereof.
Background
Zeolite molecular sieves are microporous crystalline materials with framework structures, and have the advantages of specific pore size, structural characteristics, large specific surface area, proper mechanical strength, applicability to chemical reactions and controllable selectivity to catalytic reactions, so that the zeolite molecular sieves are often applied to a variety of catalytic reactions, and particularly have wide application in petroleum refining and processing, coal chemical industry, natural gas chemical industry, biomass industry, polymer precursor preparation and the like.
The MTW structure molecular sieve material has one-dimensional linear non-crossed pore canal composed of twelve-membered ring, the size of the pore canal between the middle pore canal and the large pore molecular sieve can effectively realize shape selective catalytic conversion of most organic molecules, and the MTW structure molecular sieve has good geothermal stability, unique pore canal structure and adjustable acidity, thereby showing good catalytic activity, product selectivity and catalytic stability in a plurality of acid catalytic reactions such as alkane cracking, isomerization, reforming, aromatic alkylation and the like in the fields of petroleum refining and chemical industry.
The two (or more) molecular sieve crystals form new eutectic (intergrowth) molecular sieve crystals due to the stacking or misordering of identical or nearly infinite constituent units. The eutectic molecular sieve can modulate the pore structure and the acid property of the molecular sieve, has respective reaction characteristics of the two molecular sieves in a catalytic reaction, and shows unique synergistic effect and reaction performance different from those of a mechanical mixed sample, has attracted extensive attention in the industry, and is a research and development hotspot of the molecular sieve for current industrial catalysis.
The results of the reaction of MTW/MFI eutectic molecular sieve for catalyzing toluene and methanol to methylate to prepare xylene are reported in the literature (J.Nat.Gas chem.2007,16, 37-41), and the catalytic performance of the eutectic molecular sieve is better than that of a catalyst which is prepared from MFI, MTW and a mechanical mixture of MFI and MTW.
CN201310532438.X discloses a Beta/ZSM-12 composite molecular sieve and a synthesis method thereof, wherein the method comprises the steps of mixing an alkali source, a silicon source, an aluminum source, water and a template agent according to a certain proportion and a material mixing sequence, performing pre-crystallization, adding a ZSM-12 molecular sieve which is subjected to ultrasonic treatment by a glucose solution, and performing hydrothermal crystallization to obtain the composite molecular sieve containing the Beta and the ZSM-12.
CN201510666029.8 discloses a preparation method of a blocky Beta/ZSM-12 intergrowth molecular sieve, which adopts a solvent evaporation method to mix inorganic base, quaternary ammonium salt, a silicon source, an aluminum source and deionized water according to a certain proportion and a mixing sequence, and after stirring and aging, the solvent is evaporated, and then crystallization treatment is carried out to prepare the Beta/ZSM-12 intergrowth molecular sieve, wherein the method is characterized in that the particles are blocky and the particle size is 2-4 mu m.
CN104549466A discloses an in-situ synthesis ZSM-5/Beta intergrowth molecular sieve catalyst and a preparation method thereof, the method mixes and sprays an aluminum source, a Beta molecular sieve, a silicon source and water according to a certain proportion to form spray microspheres, and mixes the microspheres, an alkali source, the aluminum source, a template agent and water according to a certain proportion to carry out hydrothermal treatment to obtain the ZSM-5 and Beta intergrowth molecular sieve.
The existing synthesis method of the intergrowth molecular sieve has some defects, such as the composite structure and the crystal proportion of the synthesized intergrowth molecular sieve are difficult to control, the synthesis cost is high, the preparation process is complex, the type of the eutectic molecular sieve is single, and the application of the eutectic molecular sieve is influenced.
Disclosure of Invention
The invention provides a eutectic material containing an MTW structure, and solves the technical problem that the prior art cannot provide a single type of MTW/MOR eutectic molecular sieve and MTW/BEA eutectic molecular sieve products.
The second technical problem to be solved by the invention is to provide a preparation method of the eutectic material, which can be used for producing the eutectic material containing the MTW structure and overcomes the problems of complicated process and expensive raw materials in the prior art for producing the eutectic material containing the MTW structure.
In order to achieve one of the above technical problems, the present invention provides a eutectic material containing an MTW structure, which comprises, by mass, 1.2% to 98% of an MTW structure material, and the balance of BEA or MOR structure material; the Si/Al atomic ratio in the eutectic material is 1-6000.
Further, the specific surface area of the eutectic material is 90m 2 G to 810m 2 Per g, pore volume 0.02cm 3 G to 0.55cm 3 (ii) a median particle diameter of 0.1 to 30 μm/g.
Preferably, the content of the MTW structural material is 5% to 90%.
Preferably, the mass percentage content of the silicon oxide in the eutectic material is 50% to 99.99%.
In order to achieve the second technical problem, the preparation method provided by the invention comprises the following steps: 1) Mixing water, a substance containing aluminum element, a substance containing silicon element and an alkaline substance; 2) Stirring the mixture obtained in the step 1) for 0.1 to 50 hours; 3) Heating the mixture obtained in step 2) to 120 to 190 ℃, maintaining the mixture pressure at 0.1 to 15MPa, and maintaining the temperature range for 20 to 200 hours; 4) Adjusting the mixture obtained in step 3) to another temperature point different from step 3) of 130 ℃ to 200 ℃, maintaining the mixture pressure at 0.1MPa to 15MPa, and maintaining the temperature for 15 hours to 190 hours; 5) And (5) taking out the product obtained in the step 4), and separating to obtain the eutectic material containing the MTW structure.
Preferably, the substance containing aluminum element is at least one of metaaluminate, aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum hydroxide, pseudo-boehmite, kaolin and montmorillonite; the substance containing silicon element is at least one of water glass, silica sol, white carbon black, fly ash, kaolin, montmorillonite, attapulgite and tetraethoxysilane; the alkaline substance is at least one of sodium hydroxide, rubidium hydroxide, cesium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide, ammonia water, and tetraalkylammonium hydroxide.
In a further embodiment, the mixture of step 1) is alkaline and has a pH of 7.5 to 14.
Further, the stirring time in the step 2) is 0.3 to 10 hours.
In a further proposal, the temperature in the step 3) ranges from 120 ℃ to 190 ℃, the pressure ranges from 0.4MPa to 10MPa, and the time ranges from 20 hours to 150 hours.
Further, in the step 4), the temperature is in the range of 135 ℃ to 189 ℃, the pressure is in the range of 0.5MPa to 9MPa, and the time is in the range of 20 hours to 140 hours.
The invention has the beneficial effects that: the eutectic material containing the MTW structure prepared by the method has the advantages that the material particles contain the BEA or MOR structure besides the MTW structure, and the specific surface area of the eutectic material is 90m 2 G to 810m 2 Per g, pore volume 0.02cm 3 G to 0.55cm 3 Per g, the mean particle size of the eutectic material is between 0.1 and 30 μm. The eutectic material at least comprises MTW structure material, and the content of the MTW structure material is 5-90% (mass percent), wherein the content of the silicon oxide is 50-99.99% (mass percent). The preparation method of the eutectic material containing the MTW structure can be used for producing the eutectic material containing the MTW structure, and overcomes the technical problem that the MTW/MOR eutectic molecular sieve and the MTW/BEA eutectic molecular sieve cannot be provided in the prior art, and the product variety is single.
Drawings
FIG. 1 is a SEM image of the MTW/BEA zeolite molecular sieve prepared in example 1 of the invention.
FIG. 2 is an XRD pattern of the MTW/BEA zeolite molecular sieve prepared in example 1 of the present invention.
FIG. 3 is a SEM image of the MTW/MOR zeolite molecular sieve prepared in example 3 of the present invention.
FIG. 4 is an XRD pattern of the MTW/BEA zeolitic molecular sieve prepared according to example 4 of the present invention.
The invention is further described with reference to the following figures and examples.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified. Reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
(1) Preparing raw materials: 19.256g of water was added to 65.96g of a 25% tetraethylammonium hydroxide solution, 0.89g of sodium aluminate and 0.8g of potassium hydroxide were added to the solution, and 48.607g of 40% silica sol was slowly added dropwise to the solution while stirring, and stirring was continued for about 1 hour.
(2) The solution is transferred to a reaction kettle and is placed in an oven at 140 ℃ for crystallization for 48 hours.
(3) The reaction kettle is taken out and is put in an oven at 160 ℃ for crystallization for 72 hours.
(4) And (3) post-treatment process: and carrying out suction filtration or centrifugal separation on the crystallized product, washing the crystallized product with distilled water until the pH value of a product leacheate is 7-8, drying the crystallized product in an oven at the temperature of 80 ℃ for 8-12 hours, and finally heating the crystallized product to 500-600 ℃ at the speed of 1-4 ℃/in a muffle furnace to continue roasting the crystallized product for 4-6 hours to obtain the final zeolite molecular sieve product.
The content of the obtained product was 58% by mass of MTW-structured material, and the balance was BEA-structured material; the Si/Al atomic ratio in the eutectic material is 40:1, the specific surface area of the eutectic material is 510m 2 Pore volume of 0.09 cm/g 3 (ii)/g, average particle diameter is 3 μm.
Example 2
(1) Preparing raw materials: 19.256g of water was added to 20g of tetraethylammonium bromide, 0.69g of sodium aluminate and 1.2g of sodium hydroxide were added to the solution, and 68.607g of silica sol was slowly added dropwise to the solution while stirring, and stirring was continued for about 1 hour.
(2) The solution is transferred to a reaction kettle and is placed in an oven at 140 ℃ for crystallization for 48 hours.
(3) The reaction kettle is taken out and is put in an oven at 160 ℃ for crystallization for 96 hours.
(4) And carrying out suction filtration or centrifugal separation on the crystallized product, washing the crystallized product with distilled water until the pH value of a product leacheate is 7-8, drying the crystallized product in an oven at the temperature of 80 ℃ for 8-12 hours, and finally heating the crystallized product to 500-600 ℃ at the speed of 1-4 ℃/in a muffle furnace to continue roasting the crystallized product for 4-6 hours to obtain the final zeolite molecular sieve product.
The resulting product contained 37% by mass of MTW structural material, the remainder being MOR structural material; the Si/Al atomic ratio in the eutectic material is 29:1, the specific surface area of the eutectic material is 530m 2 Per g, pore volume 0.15cm 3 (g) the average particle diameter was 2 μm.
Example 3
(1) Preparing raw materials: 29.256g of water was added to 35.96g of methyltriethylammonium chloride, 0.29g of sodium aluminate and 0.9g of sodium hydroxide were added to the solution, and 50.607g of silica sol was slowly dropped into the solution while stirring, and stirring was continued for about 1 hour.
(2) The solution is transferred to a reaction kettle and is placed in an oven at 140 ℃ for crystallization for 72 hours.
(3) The reaction kettle is taken out and is placed in an oven at 160 ℃ for crystallization for 72 hours.
(4) And (3) carrying out suction filtration or centrifugal separation on the crystallized product, washing the crystallized product with distilled water until the pH value of a product leacheate is 7-8, drying the crystallized product in an oven at the temperature of 80 ℃ for 8-12 hours, and finally heating the crystallized product in a muffle furnace at the speed of 1-4 ℃/to 500-600 ℃ for continuously roasting the crystallized product for 4-6 hours to obtain a final zeolite molecular sieve mesh product.
The resulting product contains, in mass percent, 78% of MTW structural material, the remainder being MOR structural material; the Si/Al atomic ratio in the eutectic material is 89:1, the specific surface area of the eutectic material is 390m 2 Per g, pore volume 0.09cm 3 (g) the average particle diameter was 1 μm.
Example 4
(1) Preparing raw materials: 49.256g of water was added to 25.96g of tetraethylammonium iodide, 0.02g of sodium aluminate and 3g of sodium hydroxide were added to the solution, and 68.607g of silica sol was slowly added dropwise to the solution with stirring and stirring was continued for about 1 hour.
(2) The solution is transferred to a reaction kettle and is placed in an oven at 140 ℃ for crystallization for 72 hours.
(3) The reaction kettle is taken out and is put in an oven at 160 ℃ for crystallization for 96 hours.
(4) And carrying out suction filtration or centrifugal separation on the crystallized product, washing the crystallized product with distilled water until the pH value of a product leacheate is 7-8, drying the crystallized product in an oven at the temperature of 80 ℃ for 8-12 hours, and finally heating the crystallized product to 500-600 ℃ at the speed of 1-4 ℃/in a muffle furnace to continue roasting the crystallized product for 4-6 hours to obtain the final zeolite molecular sieve product.
The obtained product contains 90% of MTW structural material and the balance of BEA structural material in percentage by mass; the Si/Al atomic ratio in the eutectic material is 500:1, the specific surface area of the eutectic material is 397m 2 Per g, pore volume 0.18cm 3 (ii)/g, average particle diameter 8 μm.
Examples 5 to 20
The raw materials containing silicon, aluminum, alkaline substances and the like are operated according to the preparation conditions of table 1 and the same steps as those in the embodiments 1 to 4, and the eutectic material containing the MTW structure can be obtained.
TABLE 1
Finally, it should be emphasized that the above-described preferred embodiments of the present invention are merely examples of implementations, and it should be understood that various changes and modifications may be made by those skilled in the art, and any changes, equivalents, improvements and the like, which fall within the spirit and principle of the present invention, should be included in the scope of the present invention.
Claims (2)
1. A eutectic material containing an MTW structure, characterized by:
the preparation method of the eutectic material comprises the following steps:
1) Preparing raw materials: adding 29.256g of water into 35.96g of methyl triethyl ammonium chloride, adding 0.29g of sodium aluminate and 0.9g of sodium hydroxide into the solution, slowly dropwise adding 50.607g of silica sol into the solution while stirring, and continuously stirring for 1 hour;
2) Transferring the solution to a reaction kettle, and placing the reaction kettle in a drying oven at 140 ℃ for crystallization for 72 hours;
3) Taking out the reaction kettle, and placing the reaction kettle in a drying oven at 160 ℃ for crystallization for 72 hours;
4) Carrying out suction filtration or centrifugal separation on the crystallized product, washing the crystallized product with distilled water until the pH value of a product leacheate is 7-8, drying the product leacheate for 8-12 hours in an oven at the temperature of 80 ℃, and finally heating the product leacheate to 500-600 ℃ at the speed of 1-4 ℃/in a muffle furnace to continue roasting the product leacheate for 4-6 hours to obtain a final zeolite molecular sieve mesh product;
the content of the obtained product was 78% by mass of MTW structural material, the remainder being MOR structural material; the Si/Al atomic ratio in the eutectic material is 89:1, the specific surface area of the eutectic material is 390m 2 Per g, pore volume 0.09cm 3 (iv) g, average particle diameter 1 μm.
2. A eutectic material comprising an MTW structure, wherein:
the preparation method of the eutectic material comprises the following steps:
1) Preparing raw materials: adding 49.256g of water into 25.96g of tetraethylammonium iodide, adding 0.02g of sodium aluminate and 3g of sodium hydroxide into the solution, slowly dropwise adding 68.607g of silica sol into the solution while stirring, and continuously stirring for 1 hour;
2) Transferring the solution to a reaction kettle, and placing the reaction kettle in a drying oven at 140 ℃ for crystallization for 72 hours;
3) Taking out the reaction kettle, and placing the reaction kettle in a drying oven at 160 ℃ for crystallization for 96 hours;
4) Carrying out suction filtration or centrifugal separation on the crystallized product, washing the crystallized product with distilled water until the pH value of a product leacheate is 7-8, drying the product leacheate for 8-12 hours in an oven at the temperature of 80 ℃, and finally heating the product leacheate to 500-600 ℃ at the speed of 1-4 ℃/in a muffle furnace to continue roasting the product leacheate for 4-6 hours to obtain a final zeolite molecular sieve mesh product;
the resulting product contains, in mass percent, 90% of MTW structural material, the remainder being BEA structural material; the Si/Al atomic ratio in the eutectic material is 500:1, the specific surface area of the eutectic material is 397m 2 Per g, pore volume 0.18cm 3 (ii)/g, average particle diameter 8 μm.
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| CN101679055A (en) * | 2007-05-25 | 2010-03-24 | Ifp公司 | Novel process for preparing zeolite eu-1 |
| CN108275698A (en) * | 2018-03-19 | 2018-07-13 | 中国石油大学(北京) | A kind of Beta/ZSM-12 symbiosis zeolite molecular sieve and preparation method thereof |
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| CN101384366A (en) * | 2006-02-14 | 2009-03-11 | 埃克森美孚化学专利公司 | A high throughput process for manufacturing molecular sieves |
| CN101679055A (en) * | 2007-05-25 | 2010-03-24 | Ifp公司 | Novel process for preparing zeolite eu-1 |
| CN108275698A (en) * | 2018-03-19 | 2018-07-13 | 中国石油大学(北京) | A kind of Beta/ZSM-12 symbiosis zeolite molecular sieve and preparation method thereof |
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