Rapid and controllable preparation method of ssz-13 zeolite and h-ssz-13 zeolite and methanol-to-olefins catalyst

Abstract

The invention provides a SSZ-13 zeolite, a rapid and controllable preparation method thereof, a H-SSZ-13 zeolite and a methanol-to-olefins catalyst. The method comprises the following steps: uniformly mixing water, an organic template agent and sodium hydroxide, adding an aluminum source, stirring vigorously until the aluminum source is dissolved; sequentially adding a specific solid silicon source and crystal seeds, and aging to obtain a gel; The above-mentioned gel is subjected to crystallization treatment, and the solid phase product is separated after the crystallization is completed, and then dried and roasted to obtain SSZ‑13 zeolite. The invention also provides H-SSZ-13 zeolite and methanol-to-olefins catalyst. Compared with the existing conventional SSZ-13 zeolite preparation method, the SSZ-13 zeolite synthesized by the present invention has fast crystallization speed, high crystallinity, controllable particle size, large specific surface area and good diffusion performance. It has excellent catalytic performance and high anti-carbon deposition ability.

Description

technical field

[0001] The invention relates to a rapid and controllable preparation method of SSZ-13 zeolite, H-SSZ-13 zeolite and methanol-to-olefin catalyst, belonging to the technical field of catalyst preparation. Background technique

[0002] Low-carbon olefins such as ethylene propylene are important chemical intermediate products, widely used in synthetic plastics and petrochemical products, and occupy an extremely important position in the national economy. In my country, the traditional process of obtaining low-carbon olefins by steam cracking of petroleum hydrocarbons such as naphtha and light diesel oil is facing the challenge of ethylene-propane-to-olefins in Europe, America, and the Middle East. As my country's petroleum resources become increasingly heavy, it is difficult for my country's ethane-propane cracking process to produce olefins to make breakthroughs in a short period of time. In contrast, my country's energy structure is characterized by rich coal,...

Examples

Embodiment 1

[0052] This embodiment provides a method for preparing a methanol-to-olefins catalyst, which comprises the following steps:

[0053] Weigh 25.0g of template agent TMAdaOH (25wt%) and 0.9g of sodium hydroxide, add 89.3g of deionized water, stir and mix evenly;

[0054] Add 0.37g of aluminum hydroxide to the above solution at one time, stir vigorously for 10 minutes; then slowly add 9g of silicon source silica, stir for 30 minutes, add 0.18g of seed crystals, and continue vigorously stirring at about 30°C for 2 hours for aging ;

[0055] The obtained gel was transferred to several crystallization kettles in equal parts, and statically crystallized, the temperature was set at 160°C, and the crystallization time was 0 hour, 2 hours, 4 hours, 6 hours, 7 hours, 8 hours, 10 hours, 12 hours, 24 hours, 48 ​​hours, 72 hours, 6 days; after the crystallization is completed, the crystallization kettle is quenched with water to room temperature, the solid product in it is centrifuged and w...

Embodiment 2

[0059] This embodiment provides a method for preparing a methanol-to-olefins catalyst, which comprises the following steps:

[0060] Weigh 130.2g of template agent TMAdaOH (25wt%) and 25.6g of sodium hydroxide, add 478.5g of deionized water, place in a 30°C water bath, stir and mix evenly;

[0061] Add 5.0g of aluminum hydroxide to the above solution and stir vigorously for 10 minutes;

[0062] Add 96g of silicon source D silicon at one time, stir vigorously for 30 minutes, add 1.9g of small crystal seeds, and continue to stir and age at about 30°C for 2 hours to obtain a gel;

[0063] The obtained gel was transferred to a crystallization kettle, dynamic crystallization was performed at 20 rpm, the temperature was set at 160°C, and the crystallization time was 4 days; after the crystallization was completed, the kettle was taken out and quenched with water to room temperature, centrifuged and washed with water until neutral. The obtained sample was dried in an oven at 120°C, ...

Embodiment 3

[0067] This embodiment provides a method for preparing a methanol-to-olefins catalyst, which comprises the following steps:

[0068] Weigh 130.2g of template agent TMAdaOH (25wt%) and 25.6g of sodium hydroxide, add 478.5g of deionized water, place in a 30°C water bath, stir and mix evenly;

[0069] Add 5.0g of aluminum hydroxide to the above solution and stir vigorously for 10 minutes;

[0070] Add 96 g of solid silicon source C silicon at one time, stir vigorously for 30 minutes, add 1.9 g of small crystal seeds, and continue to stir and age at about 30 ° C for 2 hours to obtain a gel;

[0071] Transfer the obtained gel to a crystallization kettle, conduct dynamic crystallization at 20 rpm, set the crystallization temperature at 160°C, and crystallize for 4 days; after the specified crystallization time is reached, take out the crystallization kettle and quench it with water to room temperature , centrifuged and washed with water until neutral, the obtained sample was dried ...

technical field

[0001] The invention relates to a rapid and controllable preparation method of SSZ-13 zeolite, H-SSZ-13 zeolite and methanol-to-olefin catalyst, belonging to the technical field of catalyst preparation. Background technique

[0002] Low-carbon olefins such as ethylene propylene are important chemical intermediate products, widely used in synthetic plastics and petrochemical products, and occupy an extremely important position in the national economy. In my country, the traditional process of obtaining low-carbon olefins by steam cracking of petroleum hydrocarbons such as naphtha and light diesel oil is facing the challenge of ethylene-propane-to-olefins in Europe, America, and the Middle East. As my country's petroleum resources become increasingly heavy, it is difficult for my country's ethane-propane cracking process to produce olefins to make breakthroughs in a short period of time. In contrast, my country's energy structure is characterized by rich coal,...

Examples

Embodiment 1

[0052] This embodiment provides a method for preparing a methanol-to-olefins catalyst, which comprises the following steps:

[0053] Weigh 25.0g of template agent TMAdaOH (25wt%) and 0.9g of sodium hydroxide, add 89.3g of deionized water, stir and mix evenly;

[0054] Add 0.37g of aluminum hydroxide to the above solution at one time, stir vigorously for 10 minutes; then slowly add 9g of silicon source silica, stir for 30 minutes, add 0.18g of seed crystals, and continue vigorously stirring at about 30°C for 2 hours for aging ;

[0055] The obtained gel was transferred to several crystallization kettles in equal parts, and statically crystallized, the temperature was set at 160°C, and the crystallization time was 0 hour, 2 hours, 4 hours, 6 hours, 7 hours, 8 hours, 10 hours, 12 hours, 24 hours, 48 ​​hours, 72 hours, 6 days; after the crystallization is completed, the crystallization kettle is quenched with water to room temperature, the solid product in it is centrifuged and w...

Embodiment 2

[0059] This embodiment provides a method for preparing a methanol-to-olefins catalyst, which comprises the following steps:

[0060] Weigh 130.2g of template agent TMAdaOH (25wt%) and 25.6g of sodium hydroxide, add 478.5g of deionized water, place in a 30°C water bath, stir and mix evenly;

[0061] Add 5.0g of aluminum hydroxide to the above solution and stir vigorously for 10 minutes;

[0062] Add 96g of silicon source D silicon at one time, stir vigorously for 30 minutes, add 1.9g of small crystal seeds, and continue to stir and age at about 30°C for 2 hours to obtain a gel;

[0063] The obtained gel was transferred to a crystallization kettle, dynamic crystallization was performed at 20 rpm, the temperature was set at 160°C, and the crystallization time was 4 days; after the crystallization was completed, the kettle was taken out and quenched with water to room temperature, centrifuged and washed with water until neutral. The obtained sample was dried in an oven at 120°C, ...

Embodiment 3

[0067] This embodiment provides a method for preparing a methanol-to-olefins catalyst, which comprises the following steps:

[0068] Weigh 130.2g of template agent TMAdaOH (25wt%) and 25.6g of sodium hydroxide, add 478.5g of deionized water, place in a 30°C water bath, stir and mix evenly;

[0069] Add 5.0g of aluminum hydroxide to the above solution and stir vigorously for 10 minutes;

[0070] Add 96 g of solid silicon source C silicon at one time, stir vigorously for 30 minutes, add 1.9 g of small crystal seeds, and continue to stir and age at about 30 ° C for 2 hours to obtain a gel;

[0071] Transfer the obtained gel to a crystallization kettle, conduct dynamic crystallization at 20 rpm, set the crystallization temperature at 160°C, and crystallize for 4 days; after the specified crystallization time is reached, take out the crystallization kettle and quench it with water to room temperature , centrifuged and washed with water until neutral, the obtained sample was dried ...

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